Cement activator composition for treatment of subterranean formations

ABSTRACT

Various embodiments disclosed relate to cement activator compositions for treatment of subterranean formations. In various embodiments, the present invention provides a method of treating a subterranean formation including placing in the subterranean formation a liquid cement activator composition including water, an alkali sulfate salt, a polyphosphate salt, and a stabilizer polymer.

BACKGROUND

Cements play an important role in wellbore integrity. Cements may beused in primary cementing operations whereby pipe strings, such ascasing and liners, are cemented in well bores. In a typical primarycementing operation, a cement may be pumped into an annulus between theexterior surface of the pipe string disposed therein and the walls ofthe well bore (or a larger conduit in the well bore). The cement may setin the annulus, thereby forming an annular sheath of hardened,substantially impermeable material (e.g., a cement sheath) that maysupport and position the pipe string in the well bore and may bond theexterior surface of the pipe string to the well bore walls (or to thelarger conduit). Cements may also be used in remedial cementing methods,such as in squeeze cementing for sealing voids in a pipe string, cementsheath, gravel pack, subterranean formation, and the like.

A broad variety of cement compositions have been used in subterraneancementing operations. In some instances, set-delayed cement compositionshave been used. Set-delayed cement compositions are characterized byremaining in a pumpable fluid state for at least about one day (e.g., atleast about 7 days, about 2 weeks, or about 2 years or more) at roomtemperature (e.g., about 20-30° C.) in quiescent storage. When desiredfor use, the set-delayed cement compositions should be capable of beingactivated whereby reasonable compressive strengths are developed. Forexample, an activating composition can be added to a set-delayed cementcomposition whereby the composition cures (e.g., sets) into a hardenedmass.

A number of activating compositions may be employed to activate oraccelerate curing of cementitious compositions. However, within 24hours, many activating compositions exhibit separation or form a gelledmass that cannot be returned to a uniformly dispersed suspension evenwith application shear or agitation. Consequently, many activatingcompositions must be prepared immediately prior to use, which canpresent many disadvantages including operational disruptions due to theneed for having material prepared on location.

BRIEF DESCRIPTION OF THE FIGURES

The drawings illustrate generally, by way of example, but not by way oflimitation, various embodiments discussed in the present document.

FIG. 1 illustrates a system or apparatus for delivering a composition toa subterranean formation, in accordance with various embodiments.

FIG. 2 illustrates a photograph of a 7-day-old activating system, inaccordance with various embodiments.

FIG. 3 illustrates a photograph of a 7-day-old activating systemincluding a 2-acrylamido-2-methylpropane sulfonic acid(AMPS)/dimethylacrylamide (DMA) copolymer, in accordance with variousembodiments.

FIG. 4 illustrates a photograph of a 3-day-old activating systemincluding an AMPS/acrylamide/acrylonitrile copolymer and a viscosifier,in accordance with various embodiments.

FIG. 5 illustrates a photograph of a 3-day-old activating systemincluding an AMPS/DMA copolymer and viscosifier, in accordance withvarious embodiments.

FIG. 6 illustrates a photograph of a 4-day-old activating systemincluding an AMPS/DMA copolymer and a viscosifier, in accordance withvarious embodiments.

FIG. 7 illustrates a photograph of a 3-day-old activating systemincluding an AMPS/DMA copolymer and a viscosifier, in accordance withvarious embodiments.

FIG. 8 illustrates a photograph of a 3-day-old activating system, inaccordance with various embodiments.

FIG. 9 illustrates a photograph of a 3-day-old activating system, inaccordance with various embodiments.

FIG. 10 illustrates a photograph of a 24-hour-old activating systemincluding an AMPS/DMA copolymer, in accordance with various embodiments.

FIG. 11 illustrates a photograph of a 24-hour-old activating systemincluding a poly(vinyl alcohol) polymer, in accordance with variousembodiments.

FIG. 12 illustrates a photograph of a 24-hour-old activating systemincluding an acrylamide-acrylic acid copolymer, in accordance withvarious embodiments.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to certain embodiments of thedisclosed subject matter, examples of which are illustrated in part inthe accompanying drawings. While the disclosed subject matter will bedescribed in conjunction with the enumerated claims, it will beunderstood that the exemplified subject matter is not intended to limitthe claims to the disclosed subject matter.

In this document, values expressed in a range format should beinterpreted in a flexible manner to include not only the numericalvalues explicitly recited as the limits of the range, but also toinclude all the individual numerical values or sub-ranges encompassedwithin that range as if each numerical value and sub-range is explicitlyrecited. For example, a range of “about 0.1% to about 5%” or “about 0.1%to 5%” should be interpreted to include not just about 0.1% to about 5%,but also the individual values (e.g., 1%, 2%, 3%, and 4%) and thesub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within theindicated range. The statement “about X to Y” has the same meaning as“about X to about Y,” unless indicated otherwise. Likewise, thestatement “about X, Y, or about Z” has the same meaning as “about X,about Y, or about Z,” unless indicated otherwise.

In this document, the terms “a,” “an,” or “the” are used to include oneor more than one unless the context clearly dictates otherwise. The term“or” is used to refer to a nonexclusive “or” unless otherwise indicated.The statement “at least one of A and B” has the same meaning as “A, B,or A and B.” In addition, it is to be understood that the phraseology orterminology employed herein, and not otherwise defined, is for thepurpose of description only and not of limitation. Any use of sectionheadings is intended to aid reading of the document and is not to beinterpreted as limiting; information that is relevant to a sectionheading may occur within or outside of that particular section. A commacan be used as a delimiter or digit group separator to the left or rightof a decimal mark; for example, “0.000,1” is equivalent to “0.0001.”

In the methods described herein, the acts can be carried out in anyorder without departing from the principles of the invention, exceptwhen a temporal or operational sequence is explicitly recited.Furthermore, specified acts can be carried out concurrently unlessexplicit claim language recites that they be carried out separately. Forexample, a claimed act of doing X and a claimed act of doing Y can beconducted simultaneously within a single operation, and the resultingprocess will fall within the literal scope of the claimed process.

The term “about” as used herein can allow for a degree of variability ina value or range, for example, within 10%, within 5%, or within 1% of astated value or of a stated limit of a range, and includes the exactstated value or range.

The term “substantially” as used herein refers to a majority of, ormostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%,98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or100%.

The term “organic group” as used herein refers to any carbon-containingfunctional group. For example, an oxygen-containing group such as analkoxy group, aryloxy group, aralkyloxy group, oxo(carbonyl) group; acarboxyl group including a carboxylic acid, carboxylate, and acarboxylate ester; a sulfur-containing group such as an alkyl and arylsulfide group; and other heteroatom-containing groups. Non-limitingexamples of organic groups include OR, OOR, OC(O)N(R)₂, CN, CF₃, OCF₃,R, C(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR, SO₂R, SO₂N(R)₂,SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)₂,OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂N(R)C(O)R, (CH₂)₀₋₂N(R)N(R)₂,N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂,N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂,N(COR)COR, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, C(═NOR)R, and substituted orunsubstituted (C₁-C₁₀₀)hydrocarbyl, wherein R can be hydrogen (inexamples that include other carbon atoms) or a carbon-based moiety, andwherein the carbon-based moiety can itself be substituted orunsubstituted.

The term “substituted” as used herein in conjunction with a molecule oran organic group as defined herein refers to the state in which one ormore hydrogen atoms contained therein are replaced by one or morenon-hydrogen atoms. The term “functional group” or “substituent” as usedherein refers to a group that can be or is substituted onto a moleculeor onto an organic group. Examples of substituents or functional groupsinclude, but are not limited to, a halogen (e.g., F, Cl, Br, and I); anoxygen atom in groups such as hydroxy groups, alkoxy groups, aryloxygroups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groupsincluding carboxylic acids, carboxylates, and carboxylate esters; asulfur atom in groups such as thiol groups, alkyl and aryl sulfidegroups, sulfoxide groups, sulfone groups, sulfonyl groups, andsulfonamide groups; a nitrogen atom in groups such as amines,hydroxyamines, nitriles, nitro groups, N-oxides, hydrazides, azides, andenamines; and other heteroatoms in various other groups. Non-limitingexamples of substituents that can be bonded to a substituted carbon (orother) atom include F, Cl, Br, I, OR, OC(O)N(R)₂, CN, NO, NO₂, ONO₂,azido, CF₃, OCF₃, R, O (oxo), S (thiono), C(O), S(O), methylenedioxy,ethylenedioxy, N(R)₂, SR, SOR, SO₂R, SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R,C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂,(CH₂)₀₋₂N(R)C(O)R, (CH₂)₀₋₂N(R)N(R)₂, N(R)N(R)C(O)R, N(R)N(R)C(O)OR,N(R)N(R)CON(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂, N(R)C(O)OR, N(R)C(O)R,N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂, N(COR)COR, N(OR)R, C(═NH)N(R)₂,C(O)N(OR)R, and C(═NOR)R, wherein R can be hydrogen or a carbon-basedmoiety; for example, R can be hydrogen, (C₁-C₁₀₀)hydrocarbyl, alkyl,acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, orheteroarylalkyl; or wherein two R groups bonded to a nitrogen atom or toadjacent nitrogen atoms can together with the nitrogen atom or atomsform a heterocyclyl.

The term “alkyl” as used herein refers to straight chain and branchedalkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from1 to 8 carbon atoms. Examples of straight chain alkyl groups includethose with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl,n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples ofbranched alkyl groups include, but are not limited to, isopropyl,iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and2,2-dimethylpropyl groups. As used herein, the term “alkyl” encompassesn-alkyl, isoalkyl, and anteisoalkyl groups as well as other branchedchain forms of alkyl. Representative substituted alkyl groups can besubstituted one or more times with any of the groups listed herein, forexample, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, andhalogen groups.

The term “alkenyl” as used herein refers to straight and branched chainand cyclic alkyl groups as defined herein, except that at least onedouble bond exists between two carbon atoms. Thus, alkenyl groups havefrom 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12carbon atoms or, in some embodiments, from 2 to 8 carbon atoms. Examplesinclude, but are not limited to vinyl, —CH═CH(CH₃), —CH═C(CH₃)₂,—C(CH₃)═CH₂, —C(CH₃)═CH(CH₃), —C(CH₂CH₃)═CH₂, cyclohexenyl,cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienylamong others.

The term “acyl” as used herein refers to a group containing a carbonylmoiety wherein the group is bonded via the carbonyl carbon atom. Thecarbonyl carbon atom is bonded to a hydrogen forming a “formyl” group oris bonded to another carbon atom, which can be part of an alkyl, aryl,aralkyl cycloalkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl,heteroaryl, heteroarylalkyl group or the like. An acyl group can include0 to about 12, 0 to about 20, or 0 to about 40 additional carbon atomsbonded to the carbonyl group. An acyl group can include double or triplebonds within the meaning herein. An acryloyl group is an example of anacyl group. An acyl group can also include heteroatoms within themeaning herein. A nicotinoyl group (pyridyl-3-carbonyl) is an example ofan acyl group within the meaning herein. Other examples include acetyl,benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and acryloyl groups andthe like. When the group containing the carbon atom that is bonded tothe carbonyl carbon atom contains a halogen, the group is termed a“haloacyl” group. An example is a trifluoroacetyl group.

The term “aryl” as used herein refers to cyclic aromatic hydrocarbongroups that do not contain heteroatoms in the ring. Thus aryl groupsinclude, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl,indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl,naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.In some embodiments, aryl groups contain about 6 to about 14 carbons inthe ring portions of the groups. Aryl groups can be unsubstituted orsubstituted, as defined herein. Representative substituted aryl groupscan be mono-substituted or substituted more than once, such as, but notlimited to, a phenyl group substituted at any one or more of 2-, 3-, 4-,5-, or 6-positions of the phenyl ring, or a naphthyl group substitutedat any one or more of 2- to 8-positions thereof.

The term “heterocyclyl” as used herein refers to aromatic andnon-aromatic ring compounds containing three or more ring members, ofwhich one or more is a heteroatom such as, but not limited to, N, O, andS. Thus, a heterocyclyl can be a cycloheteroalkyl, or a heteroaryl, orif polycyclic, any combination thereof. In some embodiments,heterocyclyl groups include 3 to about 20 ring members, whereas othersuch groups have 3 to about 15 ring members. A heterocyclyl groupdesignated as a C₂-heterocyclyl can be a 5-ring with two carbon atomsand three heteroatoms, a 6-ring with two carbon atoms and fourheteroatoms and so forth. Likewise a C₄-heterocyclyl can be a 5-ringwith one heteroatom, a 6-ring with two heteroatoms, and so forth. Thenumber of carbon atoms plus the number of heteroatoms equals the totalnumber of ring atoms. A heterocyclyl ring can also include one or moredouble bonds. A heteroaryl ring is an embodiment of a heterocyclylgroup. The phrase “heterocyclyl group” includes fused ring speciesincluding those that include fused aromatic and non-aromatic groups.

The terms “halo,” “halogen,” or “halide” group, as used herein, bythemselves or as part of another substituent, mean, unless otherwisestated, a fluorine, chlorine, bromine, or iodine atom.

The term “haloalkyl” group, as used herein, includes mono-halo alkylgroups, poly-halo alkyl groups wherein all halo atoms can be the same ordifferent, and per-halo alkyl groups, wherein all hydrogen atoms arereplaced by halogen atoms, such as fluoro. Examples of haloalkyl includetrifluoromethyl, 1,1-dichloroethyl, 1,2-dichloroethyl,1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.

The term “hydrocarbon” or “hydrocarbyl” as used herein refers to amolecule or functional group, respectively, that includes carbon andhydrogen atoms. The term can also refer to a molecule or functionalgroup that normally includes both carbon and hydrogen atoms but whereinall the hydrogen atoms are substituted with other functional groups. Ahydrocarbyl group can be a functional group derived from a straightchain, branched, or cyclic hydrocarbon, and can be alkyl, alkenyl,alkynyl, aryl, cycloalkyl, acyl, or any combination thereof. Hydrocarbylgroups can be shown as (C_(a)-C_(b))hydrocarbyl, wherein a and b arepositive integers and mean having any of a to b number of carbon atoms.For example, (C₁-C₄)hydrocarbyl means the hydrocarbyl group can bemethyl (C₁), ethyl (C₂), propyl (C₃), or butyl (C₄), and(C₀-C_(b))hydrocarbyl means in certain embodiments there is nohydrocarbyl group.

The term “solvent” as used herein refers to a liquid that can dissolve asolid, liquid, or gas. Non-limiting examples of solvents are silicones,organic compounds, water, alcohols, ionic liquids, and supercriticalfluids.

The term “number-average molecular weight” (M_(n)) as used herein refersto the ordinary arithmetic mean of the molecular weight of individualmolecules in a sample. It is defined as the total weight of allmolecules in a sample divided by the total number of molecules in thesample. Experimentally, M_(n) is determined by analyzing a sampledivided into molecular weight fractions of species i having n_(i)molecules of molecular weight M_(i) through the formulaM_(n)=ΣM_(i)n_(i)/Σn_(i). The M_(n) can be measured by a variety ofwell-known methods including gel permeation chromatography,spectroscopic end group analysis, and osmometry. If unspecified,molecular weights of polymers given herein are number-average molecularweights.

The term “weight-average molecular weight” as used herein refers toM_(w), which is equal to ΣM_(i) ²n_(i)/ΣM_(i)n_(i), where n_(i) is thenumber of molecules of molecular weight M_(i). In various examples, theweight-average molecular weight can be determined using lightscattering, small angle neutron scattering, X-ray scattering, andsedimentation velocity.

The term “room temperature” as used herein refers to a temperature ofabout 15° C. to 28° C.

The term “standard temperature and pressure” as used herein refers to20° C. and 101 kPa.

As used herein, “degree of polymerization” is the number of repeatingunits in a polymer.

As used herein, the term “polymer” refers to a molecule having at leastone repeating unit and can include copolymers.

The term “copolymer” as used herein refers to a polymer that includes atleast two different repeating units. A copolymer can include anysuitable number of repeating units.

The term “downhole” as used herein refers to under the surface of theearth, such as a location within or fluidly connected to a wellbore.

As used herein, the term “cementing fluid” refers to fluids or slurriesused during cementing operations of a well. For example, a cementingfluid can include an aqueous mixture including at least one of cementand cement kiln dust. In another example, a cementing fluid can includea curable resinous material such as a polymer that is in an at leastpartially uncured state.

As used herein, the term “water control material” refers to a solid orliquid material that interacts with aqueous material downhole, such thathydrophobic material can more easily travel to the surface and such thathydrophilic material (including water) can less easily travel to thesurface. A water control material can be used to treat a well to causethe proportion of water produced to decrease and to cause the proportionof hydrocarbons produced to increase, such as by selectively bindingtogether material between water-producing subterranean formations andthe wellbore while still allowing hydrocarbon-producing formations tomaintain output.

As used herein, the term “fluid” refers to liquids and gels, unlessotherwise indicated.

As used herein, the term “subterranean material” or “subterraneanformation” refers to any material under the surface of the earth,including under the surface of the bottom of the ocean. For example, asubterranean formation or material can be any section of a wellbore andany section of a subterranean petroleum- or water-producing formation orregion in fluid contact with the wellbore. Placing a material in asubterranean formation can include contacting the material with anysection of a wellbore or with any subterranean region in fluid contacttherewith. Subterranean materials can include any materials placed intothe wellbore such as cement, drill shafts, liners, tubing, casing, orscreens; placing a material in a subterranean formation can includecontacting with such subterranean materials. In some examples, asubterranean formation or material can be any below-ground region thatcan produce liquid or gaseous petroleum materials, water, or any sectionbelow-ground in fluid contact therewith. For example, a subterraneanformation or material can be at least one of an area desired to befractured, a fracture or an area surrounding a fracture, and a flowpathway or an area surrounding a flow pathway, wherein a fracture or aflow pathway can be optionally fluidly connected to a subterraneanpetroleum- or water-producing region, directly or through one or morefractures or flow pathways.

As used herein, “treatment of a subterranean formation” can include anyactivity directed to extraction of water or petroleum materials from asubterranean petroleum- or water-producing formation or region, forexample, including drilling, stimulation, hydraulic fracturing,clean-up, acidizing, completion, cementing, remedial treatment,abandonment, and the like.

As used herein, a “flow pathway” downhole can include any suitablesubterranean flow pathway through which two subterranean locations arein fluid connection. The flow pathway can be sufficient for petroleum orwater to flow from one subterranean location to the wellbore orvice-versa. A flow pathway can include at least one of a hydraulicfracture, and a fluid connection across a screen, across gravel pack,across proppant, including across resin-bonded proppant or proppantdeposited in a fracture, and across sand. A flow pathway can include anatural subterranean passageway through which fluids can flow. In someembodiments, a flow pathway can be a water source and can include water.In some embodiments, a flow pathway can be a petroleum source and caninclude petroleum. In some embodiments, a flow pathway can be sufficientto divert from a wellbore, fracture, or flow pathway connected theretoat least one of water, a downhole fluid, or a produced hydrocarbon.

In various embodiments, salts having a positively charged counterion caninclude any suitable positively charged counterion. For example, thecounterion can be ammonium(NH₄ ⁺), or an alkali metal such as sodium(Na⁺), potassium (K⁺), or lithium (Li⁺). In some embodiments, thecounterion can have a positive charge greater than +1, which can in someembodiments complex to multiple ionized groups, such as Zn²⁺, Al³⁺, oralkaline earth metals such as Ca²⁺ or Mg²⁺.

In various embodiments, salts having a negatively charged counterion caninclude any suitable negatively charged counterion. For example, thecounterion can be a halide, such as fluoride, chloride, iodide, orbromide. In other examples, the counterion can be nitrate, hydrogensulfate, dihydrogen phosphate, bicarbonate, nitrite, perchlorate,iodate, chlorate, bromate, chlorite, hypochlorite, hypobromite, cyanide,amide, cyanate, hydroxide, permanganate. The counterion can be aconjugate base of any carboxylic acid, such as acetate or formate. Insome embodiments, a counterion can have a negative charge greater than−1, which can in some embodiments complex to multiple ionized groups,such as oxide, sulfide, nitride, arsenate, phosphate, arsenite, hydrogenphosphate, sulfate, thio sulfate, sulfite, carbonate, chromate,dichromate, peroxide, or oxalate.

The polymers described herein can terminate in any suitable way. In someembodiments, the polymers can terminate with an end group that isindependently chosen from a suitable polymerization initiator, —H, —OH,a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl (e.g., (C₁-C₁₀)alkylor (C₆-C₂₀)aryl) interrupted with 0, 1, 2, or 3 groups independentlyselected from the group consisting of —O—, substituted or unsubstituted—NH—, and —S—, a poly(substituted or unsubstituted(C₁-C₂₀)hydrocarbyloxy), and a poly(substituted or unsubstituted(C₁-C₂₀)hydrocarbylamino).

In various embodiments, the present invention provides a method oftreating a subterranean formation. The method includes placing in thesubterranean formation a liquid cement activator composition includingwater, an alkali sulfate salt, a polyphosphate salt, and a stabilizerpolymer. The stabilizer polymer includes a repeating group that is anethylene substituted with a group selected from the group consisting of—C(O)OH, a salt thereof, a substituted or unsubstituted(C₁-C₂₀)hydrocarbyl ester thereof; —C(O)NR¹ ₂, wherein at eachoccurrence R¹ is independently selected from the group consisting of asubstituted or unsubstituted (C₁-C₂₀)hydrocarbyl; —CN; and combinationsthereof. At each occurrence the ethylene is independently furthersubstituted or unsubstituted. The stabilizer polymer also includes arepeating group that includes an anionic group.

In various embodiments, the present invention provides a method oftreating a subterranean formation. The method includes placing in thesubterranean formation a composition including a liquid cement activatorcomposition. The liquid cement activator composition includes water, analkali sulfate salt, a polyphosphate salt, and a stabilizer polymer. Thewater is about 30 wt % to about 95 wt % of the liquid cement activatorcomposition. The alkali sulfate salt is about 0.001 wt % to about 40 wt% of the liquid cement activator composition. The polyphosphate salt isabout 0.001 wt % to about 30 wt % of the liquid cement activatorcomposition. The stabilizer polymer is about 0.001 wt % to about 30 wt %of the liquid cement activator composition. The stabilizer polymerincludes repeating groups having the structure:

At each occurrence, the repeating units independently occur in thedirection shown or in the opposite direction. The repeating units have ablock or random copolymer arrangement. The variables R², R³, and R⁴ areindependently selected from the group consisting of —H, and substitutedor unsubstituted (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groupsindependently selected from the group consisting of —O—, —S—,substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n1)—, and—(CH₂—CH₂—CH₂—O)_(n1)—, wherein n1 is about 1 to about 10,000. Thevariable R⁵ is independently selected from the group consisting ofC(O)OH, a salt thereof, a substituted or unsubstituted(C₁-C₂₀)hydrocarbyl ester thereof; —C(O)NR¹ ₂, wherein at eachoccurrence R¹ is independently selected from the group consisting of asubstituted or unsubstituted (C₁-C₂₀)hydrocarbyl; and —CN. The variableA is selected from the group consisting of —O— and —NR⁹—. The variablesR⁶, R⁷, R⁸, R⁹ are independently selected from the group consisting of—H, and a substituted or unsubstituted (C₁-C₅₀)hydrocarbyl interruptedby 0, 1, 2, or 3 groups independently selected from the group consistingof —O—, —S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n2)—, and—(CH₂—CH₂—CH₂—O)_(n2)—, wherein n2 is about 1 to about 10,000. Thevariable L¹ is selected from the group consisting of a bond and asubstituted or unsubstituted (C₁-C₅₀)hydrocarbylene interrupted by 0, 1,2, or 3 groups independently selected from the group consisting of —O—,—S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n3)—, and—(CH₂—CH₂—CH₂—O)_(n3)—, wherein n3 is about 1 to about 10,000. Thevariable AG is the anionic group. Repeating group A is about 0.001 mol %to about 25 mol % of the stabilizer polymer. Repeating group B is about25 mol % to about 99.999 mol % of the stabilizer polymer.

In various embodiments, the present invention provides a method oftreating a subterranean formation. The method includes placing in thesubterranean formation a liquid cement activator composition includingwater, an alkali sulfate salt, a polyphosphate salt, and a stabilizerpolymer. The water is about 30 wt % to about 95 wt % of the liquidcement activator composition. The alkali sulfate salt is about 0.001 wt% to about 40 wt % of the liquid cement activator composition. Thepolyphosphate salt is about 0.001 wt % to about 30 wt % of the liquidcement activator composition. The stabilizer polymer is about 0.001 wt %to about 30 wt % of the liquid cement activator composition. Thestabilizer polymer includes repeating groups having the structure:

At each occurrence, the repeating units independently occur in thedirection shown or in the opposite direction. The repeating units have ablock or random copolymer arrangement. The —S(O)(O)OH group is in theform of an acid or a salt thereof. Repeating group A is about 0.001 mol% to about 25 mol % of the stabilizer polymer. Repeating group B isabout 25 mol % to about 99.999 mol % of the stabilizer polymer.

In various embodiments, the present invention provides a systemincluding a tubular disposed in a subterranean formation. The systemalso includes a pump configured to pump a liquid cement activatorcomposition in the subterranean formation through the tubular. Thecement activator composition includes water, an alkali sulfate salt, apolyphosphate salt, and a stabilizer polymer. The stabilizer polymerincludes a repeating group that is an ethylene substituted with a groupselected from the group consisting of —C(O)OH, a salt thereof, asubstituted or unsubstituted (C₁-C₂₀)hydrocarbyl ester thereof; —C(O)NR¹₂, wherein at each occurrence R¹ is independently selected from thegroup consisting of a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl;—CN; and combinations thereof. At each occurrence the ethylene isindependently further substituted or unsubstituted. The stabilizerpolymer also includes a repeating group that includes an anionic group.

In various embodiments, the present invention provides a liquid cementactivator composition for treatment of a subterranean formation. Thecement activator composition includes water, an alkali sulfate salt, apolyphosphate salt, and a stabilizer polymer. The stabilizer polymerincludes a repeating group that is an ethylene substituted with a groupselected from the group consisting of —C(O)OH, a salt thereof, asubstituted or unsubstituted (C₁-C₂₀)hydrocarbyl ester thereof; —C(O)NR¹₂, wherein at each occurrence R¹ is independently selected from thegroup consisting of a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl;and —CN. At each occurrence the ethylene is independently furthersubstituted or unsubstituted. The stabilizer polymer also includes arepeating group that includes an anionic group.

In various embodiments, the present invention provides a liquid cementactivator composition for treatment of a subterranean formation. Thecement activator composition includes includes water, an alkali sulfatesalt, a polyphosphate salt, and a stabilizer polymer. The water is about30 wt % to about 95 wt % of the liquid cement activator composition. Thealkali sulfate salt is about 0.001 wt % to about 40 wt % of the liquidcement activator composition. The polyphosphate salt is about 0.001 wt %to about 30 wt % of the liquid cement activator composition. Thestabilizer polymer is about 0.001 wt % to about 30 wt % of the liquidcement activator composition. The stabilizer polymer includes repeatinggroups having the structure:

At each occurrence, the repeating units independently occur in thedirection shown or in the opposite direction. The repeating units have ablock or random copolymer arrangement. The variables R², R³, and R⁴ areindependently selected from the group consisting of —H, and substitutedor unsubstituted (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groupsindependently selected from the group consisting of —O—, —S—,substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n1)—, and—(CH₂—CH₂—CH₂—O)_(n1)—, wherein n1 is about 1 to about 10,000. Thevariable R⁵ is independently selected from the group consisting ofC(O)OH, a salt thereof, a substituted or unsubstituted(C₁-C₂₀)hydrocarbyl ester thereof; —C(O)NR¹ ₂, wherein at eachoccurrence R¹ is independently selected from the group consisting of asubstituted or unsubstituted (C₁-C₂₀)hydrocarbyl; and —CN. The variableA is selected from the group consisting of —O— and —NR⁹—. The variablesR⁶, R⁷, R⁸, R⁹ are independently selected from the group consisting of—H, and a substituted or unsubstituted (C₁-C₅₀)hydrocarbyl interruptedby 0, 1, 2, or 3 groups independently selected from the group consistingof —O—, —S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n2)—, and—(CH₂—CH₂—CH₂—O)_(n2)—, wherein n2 is about 1 to about 10,000. Thevariable L¹ is selected from the group consisting of a bond and asubstituted or unsubstituted (C₁-C₅₀)hydrocarbylene interrupted by 0, 1,2, or 3 groups independently selected from the group consisting of —O—,—S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O—)_(n3)—, and—(CH₂—CH₂—CH₂—O)_(n3)—, wherein n3 is about 1 to about 10,000. Thevariable AG is the anionic group. Repeating group A is about 0.001 mol %to about 99.999 mol % of the stabilizer polymer. Repeating group B isabout 0.001 mol % to about 99.999 mol % of the stabilizer polymer.

In various embodiments, the present invention provides a method ofpreparing a composition for treatment of a subterranean formation. Themethod includes forming a liquid cement activator composition fortreatment of a subterranean formation (e.g., for combining with andactivating a cement composition above-surface or downhole, for curingthe cement composition in the subterranean formation). The cementactivator composition includes water, an alkali sulfate salt, apolyphosphate salt, and a stabilizer polymer. The stabilizer polymerincludes a repeating group that is an ethylene substituted with a groupselected from the group consisting of —C(O)OH, a salt thereof, asubstituted or unsubstituted (C₁-C₂₀)hydrocarbyl ester thereof; —C(O)NR¹₂, wherein at each occurrence R¹ is independently selected from thegroup consisting of a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl;and —CN. At each occurrence the ethylene is independently furthersubstituted or unsubstituted. The stabilizer polymer also includes arepeating group that includes an anionic group.

Various embodiments of the cement activator composition and method ofusing the same have advantages over other cement activator compositionsand methods of using the same, at least some of which are unexpected.For example, in various embodiments, the cement activator compositioncan activate or accelerate curing of a wide variety of cementcompositions, such as Portland cement compositions and lime-pozzolancement compositions, such as set-delayed lime-pozzolan cementcompositions. In some embodiments, the activator composition can havegreater stability of the homogeneity of the composition, and lessgelling, for longer periods, as compared to other activatorcompositions. In various embodiments, the increased stability of theactivator composition can be independent of the viscosity of theactivator composition. In various embodiments, the greater stability ofthe activator composition can allow it to be pre-formulated and storedfor longer periods of time while remaining homogeneous, ungelled, andready for use. In various embodiments, the greater stability of theactivator composition can allow preparation of the activator compositionat a convenient location and then transportation to the job site, whichcan reduce capital expenditures due to a reduction in the need foron-site bulk storage and mixing equipment, such as for offshorecementing operations where space onboard the vessels can be limited.

Due to limitations associated with the hydration reactivity of manyset-delayed compositions, most cement activating compositions can onlybe used in temperatures above 60° C. in order for the activated cementcompositions to develop adequate strength. However, in variousembodiments, the activator composition can provide low temperature(e.g., below 60° C.) activation of cement compositions.

In some embodiments, the activator composition can have fluid losscontrol properties. Some cement compositions cannot be formulated withfluid loss control agents, either as a dry-blend or in a storable slurrystate, or can only be formulated with a limited type and concentrationof fluid loss control agents, such as due to limitations related toslurry rheology in storage. For example, addition of a fluid losscontrol agent to a set-delayed cement composition can cause undesirableeffects in the cement composition slurry during the storage period. Invarious embodiments, the activator composition can impart fluid losscontrol properties to a cement composition activated therewith. Invarious embodiments, the fluid loss control properties provided by theactivator composition can avoid on-site blending of fluid loss controlmaterials with cement slurries.

Method of Treating a Subterranean Formation.

In some embodiments, the present invention provides a method of treatinga subterranean formation. The method includes placing a liquid cementactivator composition in a subterranean formation, such as anyembodiment of the cement activator composition described herein. Theplacing of the cement activator composition in the subterraneanformation can include contacting the cement activator composition andany suitable part of the subterranean formation, or contacting thecement activator composition and a subterranean material, such as anysuitable subterranean material. The subterranean formation can be anysuitable subterranean formation. In some examples, the placing of thecement activator composition in the subterranean formation includescontacting the cement activator composition with or placing the cementactivator composition in at least one of a fracture, at least a part ofan area surrounding a fracture, a flow pathway, an area surrounding aflow pathway, and an area desired to be fractured. The placing of thecement activator composition in the subterranean formation can be anysuitable placing and can include any suitable contacting between thesubterranean formation and the cement activator composition.

In some embodiments, the method includes obtaining or providing thecement activator composition. The obtaining or providing of the cementactivator composition can occur at any suitable time and at any suitablelocation. The obtaining or providing of the cement activator compositioncan occur above the surface (e.g., one or more components of the cementactivator composition can be combined above the surface). The obtainingor providing of the cement activator composition can occur in thesubterranean formation (e.g., one or more components of the cementactivator composition can be combined downhole).

In various embodiments, the method can include combining the cementactivator composition with a cement composition. The combining can occurabove surface, such that the placing of the cement activator compositionin the subterranean formation includes placing a mixture of the cementactivator composition and the cement composition in the subterraneanformation. The combining can occur in the subterranean formation, suchthat a mixture of the cement activator composition and the cementcomposition is formed in the subterranean formation. The mixture of thecement activator composition and the cement composition can be a curablecomposition that can cure and harden. Any suitable amount of the mixtureof the cement activator composition and the cement composition can bethe cement activator composition, such as about 0.001 wt % to about99.999 wt % of the combination of the cement activator composition andthe cement composition, or about 10 wt % to about 50 wt %, or about0.001 wt % or less, or less than, equal to, or greater than about 0.01wt %, 0.1, 1, 2, 3, 4, 5, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30,32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 55, 60, 65, 70, 75, 80, 82, 84,86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99 wt %, orabout 99.999 wt % or more. In the mixture of the cement activatorcomposition and a pumice-containing (e.g., pozzolan-containing) cementcomposition, the amount of the cement activator composition can be anysuitable percent of the total weight of the pumice in the cementcomposition, such as about 0.001% to about 99.999%, about 60% to about95%, about 70% to about 90%, or about 0.001% or less, or less than,equal to, or greater than about 0.01%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15,20, 25, 30, 35, 40, 45, 50, 55, 60, 62, 64, 66, 68, 70, 71, 72, 73, 74,75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92,93, 94, 95, 93, 97, 98, 99, 99.9, 99.99%, or about 99.999% or more.

In various embodiments, the method can include curing (e.g., hardening)a mixture that includes the cement activator composition and a cementcomposition, such as a pumice-containing (e.g., pozzolan-containing)cement composition. The curing can occur for any suitable time, at anysuitable temperature, and at any suitable pressure, such as temperaturesand pressures experienced downhole. Curing can occur for less than,equal to, or greater than 10 minutes, 20, 30, 40, 50 minutes, 1 hour,1.5, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22 hours, 1 day, 1.5, 2,3, 4, 5, 6 days, 1 week, 1.5, 2, 3 weeks, or about 1 month or more.Curing can occur at about 0° C. to about 500° C., or about 20° C. toabout 400° C., or about 0° C. or less, or less than, equal to, orgreater than about 10° C., 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90,100, 125, 150, 175, 200, 225, 250, 275, 300, 350, 400, 450, or about500° C. or more.

The cured product of the mixture including the cement activatorcomposition and the cement composition can have any suitable tensilestrength, such as about 100 psi to about 10,000 psi, about 500 psi toabout 1,000 psi, or about 100 psi or less, or about 150 psi, 200, 250,300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 1,000,1,500, 2,000, 2,500, 5,000, 7,500, or about 10,000 psi or more.

The cured product of the mixture including the cement activatorcomposition and the cement composition can have any suitable compressivestrength, such as about 50 psi to about 10,000 psi, about 300 psi toabout 10,000 psi, about 1,000 psi to about 3,000 psi, about 100 psi toabout 500 psi, or about 50 psi or less, or about 75 psi, 100, 125, 150,175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 450, 500, 600, 700,800, 900, 1,000, 1,500, 2,000, 2,500, 3,000, 5,000, 7,500, or about10,000 psi or more.

In various embodiments, the method includes cementing or repairing awellbore in the subterranean formation. For example, the cementactivator composition can be placed into an annulus between a casing andthe wellbore, or between two casings, combined with a cementcomposition, and the mixture can then be cured. The mixture of thecement activator composition and the cement composition can be formedbefore placing the cement activator composition in the annulus, suchthat a mixture of the cement activator composition and the cementcomposition is placed in the annulus. In another embodiment, a cementcomposition can be placed in the annulus, and the cement activatorcomposition can be added to the cement composition in the annulus toform the mixture, which can then be cured. In some examples, the methodcan include placing a mixture of the cement activator composition and acement composition into a damaged region of a wellbore and then curingthe mixture of the cement activator composition and the cementcomposition. The cement composition can either be mixed with the cementactivator composition prior to placement in the desired location ofcuring or the cement composition can be already in-place downhole andthe cement activator composition can be combined therewith.

In various embodiments, the method includes consolidating particulatesdownhole. For example, the method can include placing a mixture of thecement activator composition and a cement composition into a region ofthe subterranean formation that includes fines, gravel, or otherparticles, and allowing the mixture to cure such that the particles aresubstantially fixed in-place. In various embodiments, the method caninclude lost-circulation management, such as by placing a mixture of thecement activator composition and a cement composition in a subterraneanregion experiencing fluid loss and curing the composition. The cementcomposition can either be mixed with the cement activator compositionprior to placement in the desired location of curing or the cementcomposition can be already in-place downhole and the cement activatorcomposition can be combined therewith.

Cement Composition.

In various embodiments, the cement activator composition can be combinedwith a cement composition. The cement composition can be any suitablecement composition that can undergo curing to form a cured cement, suchas curing after combination with the cement activator composition. Thecement composition can include any suitable type of cement, such as ahydraulic cement. The cement composition can include a cement includingcalcium, aluminum, silicon, oxygen, iron, or sulfur, which can set andharden by reaction with water. The cement composition can includePortland cement, pozzolana cement, gypsum cement, high alumina contentcement, slag cement, silica cement, or a combination thereof. In someembodiments, the Portland cements that are suitable for use inembodiments of the present invention are classified as Classes A, C, H,and G cements according to the American Petroleum Institute, APISpecification for Materials and Testing for Well Cements, APISpecification 10, Fifth Ed., Jul. 1, 1990. The cement composition caninclude pozzolana cement, such as pozzolana-lime cement. The cementcomposition can be a delayed-set cement composition. The cementcomposition can include any suitable amount of cement therein, such asabout 10 wt % to about 100 wt %, or about 10 wt % or less, or less than,equal to, or more than about 12 wt %, 14, 16, 18, 20, 25, 30, 35, 40,45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98,or about 99 wt % or more. The cement composition can be a dry cementcomposition, or a slurry (e.g., including water). A slurry cementcomposition can include any suitable amount of water, such as about 10wt % to about 95 wt %, or less than, equal to, or greater than about 12wt %, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,85, 90, 91, 92, 93, 94 wt %, or about 95 wt % or more.

A cement composition can include cement kiln dust. The cement kiln dustcan be any suitable cement kiln dust. Cement kiln dust can be formedduring the manufacture of cement and can be partially calcined kiln feedthat is removed from the gas stream and collected in a dust collectorduring a manufacturing process. Cement kiln dust can be advantageouslyutilized in a cost-effective manner since kiln dust is often regarded asa low value waste product of the cement industry. Some embodiments ofthe cement composition can include cement kiln dust but no cement,cement kiln dust and cement, or cement but no cement kiln dust. A cementkiln dust can be present in an amount of about 0.001 wt % to about 95 wt%, or about 0.001 wt % or less, or less than, equal to, or greater thanabout 0.01%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45,50, 55, 60, 65, 70, 75, 80, 85, 90 wt %, or about 95 wt % or more.

Optionally, other additives can be added to a cement or kilndust-containing composition of embodiments of the present invention asdeemed appropriate by one skilled in the art, with the benefit of thisdisclosure. Any optional ingredient listed in this paragraph can beeither present or not present in the composition or a mixture includingthe same. For example, the composition can include fly ash, metakaolin,shale, zeolite, set retarding additive, surfactant, a gas, accelerators,weight reducing additives, heavy-weight additives, lost circulationmaterials, filtration control additives, dispersants, and combinationsthereof. In some examples, additives can include crystalline silicacompounds, amorphous silica, salts, fibers, hydratable clays,microspheres, pozzolan lime, thixotropic additives, combinationsthereof, and the like.

Cement Activator Composition.

The liquid (e.g., heterogeneous or homogeneous liquid) cement activatorcomposition can be combined with a cement composition to produce amixture that can set and cure to a hardened material. The cementactivator composition can be stable, substantially avoiding separation(e.g., substantially remaining homogeneous) and substantially avoidinggelling (e.g., substantially avoiding an increase in viscosity), such asfor about 1 day to about 5 years or more, for about 1 day to about 5months, for about 1 day to about 5 weeks, or for at least about 1 day orless, or for at least about 2 days, 3, 4, 5, 6 days, 1 week, 1.5, 2,2.5, 3 weeks, 1 month, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 months, 1year, 1.5, 2, 3, 4, or for about 5 years or more.

The cement activator composition can include water. The water can be anysuitable water, such as fresh water, brine, produced water, flowbackwater, brackish water, sea water, or a combination thereof. The watercan form any suitable proportion of the cement activator composition,such as about 30 wt % to about 95 wt % of the cement activatorcomposition, 60 wt % to about 80 wt %, or about 30 wt % or less, or lessthan, equal to, or greater than about 35 wt %, 40, 45, 50, 55, 60, 62,64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 82,84, 86, 88, 90 wt %, or about 95 wt % or more of the cement activatorcomposition. In a mixture including the cement activator composition anda cement composition including pumice, the water in the cement activatorcomposition can be any suitable percent of the total weight of pumice,such as about 10% to about 90%, about 40% to about 80%, or about 10% orless, or less than, equal to, or greater than about 15%, 20, 25, 30, 35,40, 42, 44, 46, 48, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 62, 64,66, 68, 70, 75, 80, 85%, or about 90% or more. The liquid cementactivator composition can be an aqueous composition, wherein the balanceof the composition is water (e.g., aside from the alkali sulfate salt,the polyphosphate salt, the stabilizer polymer, and any othercomponents, the composition can be water).

The cement activator composition can include an alkali sulfate salt. Theactivator composition can include one alkali sulfate salt, or more thanone alkali sulfate salt. The alkali sulfate salt can be any suitablealkali sulfate salt, such that the cement activator composition can beused as described herein, such as potassium sulfate, calcium sulfate,lithium sulfate, sodium sulfate, or a combination thereof. The alkalisulfate salt can be sodium sulfate. The one or more alkali sulfate saltscan be any suitable proportion of the cement activator composition, suchas about 0.001 wt % to about 40 wt % of the cement activatorcomposition, about 1 wt % to about 15 wt %, or about 0.001 wt % or less,or less than, equal to, or more than about 0.01 wt %, 0.1, 1, 2, 3, 4,5, 5.5, 6, 6.5, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.5,9, 9.5, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, or about 40 wt % or moreof the cement activator composition. In a mixture including the cementactivator composition and a cement composition including pumice, the oneor more alkali sulfate salts can be any suitable percent of the totalweight of pumice, such as about 0.001% to about 20%, or about 0.1% toabout 5%, or about 0.001% or less, or less than, equal to, or more thanabout 0.01%, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2,1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4,3.6, 3.8, 4, 4.5, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18%, or about 20% ormore.

The cement activator composition can include a polyphosphate salt. Thecement activator composition can include one polyphosphate salt or morethan one polyphosphate salt. The polyphosphate salt can be any suitablepolyphosphate salt, such that the cement activator composition can beused as described herein. For example, the polyphosphate salt can be apolymeric metaphosphate salt, a phosphate salt, or a combinationthereof. The polyphosphate salt can be sodium hexametaphosphate, sodiumtrimetaphosphate, sodium tetrametaphosphate, sodium pentametaphosphate,sodium heptametaphosphate, sodium octametaphosphate, and combinationsthereof. The polyphosphate salt can be sodium hexametaphosphate. The oneor more polyphosphate salts can be any suitable proportion of the cementactivator composition, such as about 0.001 wt % to about 30 wt % of thecement activator composition, about 1 wt % to about 15 wt %, or about0.001 wt % or less, or less than, equal to, or greater than about 0.01wt %, 0.1, 1, 1.5, 2, 2.5, 3, 3.5, 3.6, 3.8, 4, 4.1, 4.2, 4.3, 4.4, 4.5,4.6, 4.7, 4.8, 4.9, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.5, 7, 7.5, 8, 8.5, 9,10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 24, 26, 28, or about 30 wt % ormore. In a mixture including the cement activator and a cementcomposition including pumice, the one or more polyphosphate salts can beany suitable percent of the weight of pumice therein, such as about0.001% to about 20%, about 0.01% to about 10%, or about 0.001% or less,or less than, equal to, or greater than about 0.01%, 0.05%, 0.1, 0.2,0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7,1.8, 1.9, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 12,14, 16, 18, or about 20% or more.

The cement activator composition can include an optional dispersant; insome embodiments, the cement activator composition includes one or moredispersants, while in other embodiments, the cement activatorcomposition can be free of dispersants. The dispersant can be anysuitable dispersant such that the cement activator composition can beused as described herein. The dispersant can contribute to maintainingdesirable slurry rheology when the cement composition is activated bythe cement activator composition. The dispersant can influencethickening time of the cement slurry. The dispersant can be asuperplasticizing dispersant, a sulfonated-formaldehyde-based dispersant(e.g., CFR-3™ available from Halliburton), a polycarboxylated etherdispersant, or a combination thereof. The dispersant can be apolycarboxylated ether, such as Liquiment® 514L or 5581F available fromBASF. The one or more dispersants can form any suitable proportion ofthe cement activator composition, such as about 0.001 wt % to about 40wt % of the cement activator composition, about 1 wt % to about 25 wt %,or about 0.001 wt % or less, or less than, equal to, or greater thanabout 0.01 wt %, 0.1, 1, 2, 4, 6, 7, 8, 8.5, 9, 9.5, 10, 10.2, 10.4,10.6, 10.8, 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9,12, 12.2, 12.4, 12.6, 12.8, 13, 13.5, 14, 14.5, 15, 16, 17, 18, 19, 20,22, 24, 26, 28, 30, 35, or about 40 wt % or more of the cement activatorcomposition. In a mixture including the cement activator and a cementcomposition including pumice, the one or more dispersants can be anysuitable percent of the weight of pumice therein, such as about 0.001%to about 20%, about 0.01% to about 10%, or about 0.001% or less, or lessthan, equal to, or greater than about 0.01%, 0.05%, 0.1, 0.2, 0.3, 0.4,0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1,2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.5,5, 6, 7, 8, 9, 10, 12, 14, 16, 18, or about 20% or more.

The cement activator composition can include a stabilizer polymer. Thecement activator composition can include one stabilizer polymer or morethan one stabilizer polymer. The stabilizer polymer can include arepeating group that is an ethylene substituted with a group selectedfrom the group consisting of —C(O)OH, a salt thereof, a substituted orunsubstituted (C₁-C₂₀)hydrocarbyl ester thereof; —C(O)NR¹ ₂, wherein ateach occurrence R¹ is independently selected from the group consistingof a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl; and —CN. At eachoccurrence the ethylene can be independently further substituted orunsubstituted. The stabilizer polymer can also include a repeating groupthat includes an anionic group. The one or more stabilizer polymer canform any suitable proportion of the cement activator composition, suchthat the cement activator composition can be used as described herein,such as about 0.001 wt % to about 30 wt % of the activator composition,about 0.1 wt % to about 10 wt %, or about 0.001 wt % or less, or lessthan, equal to, or greater than about 0.01 wt %, 0.1, 0.5, 1, 1.2, 1.4,1.6, 1.8, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2,3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.5, 6, 7,8, 9, 10, 12, 14, 16, 18, 20, 25, or about 30 wt % or more. In a mixtureincluding the cement activator and a cement composition includingpumice, the one or more stabilizer polymers can be any suitable percentof the weight of pumice therein, such as about 0.001% to about 20%,about 0.01% to about 10%, about 0.1% to about 2.5%, or about 0.001% orless, or less than, equal to, or greater than about 0.01%, 0.05%, 0.1,0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.5, 1.6, 1.7, 1.8,1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.2, 3.4, 3.6,3.8, 4, 4.5, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, or about 20% or more.

Without being limited to any particular mechanism of action, in variousembodiments, the combination of the alkali sulfate salt and thepolyphosphate salt can create a synergy that provides better resultsthan the singular use of either component. The alkali sulfated salt canprovide alkali hydroxide upon reaction with lime, which can cause a risein the pH of the slurry and consequently an increase in the rate ofdissolution of silicon dioxide. Cement hydration rate can have a directrelationship with the proportion of free silicates and/oraluminosilicates. The polyphosphate salt can interact through achelation mechanism that contributes to dissociation of retardingspecies from the surfaces of cementitious species, which cansubsequently increase the rate of dissolution of inhibiting calciumcomplexes. However, without the presence of the stabilizer polymerdescribed herein, the combination of the alkali sulfate salt and thepolyphosphate salt cannot maintain homogeneity in the activatorcomposition over long periods.

The repeating group that is a substituted ethylene can form any suitableproportion of the stabilizer polymer, such that the activatorcomposition can be used as described herein, such as about 0.001 mol %to about 99.999 mol %, 0.001 mol % to about 25 mol %, or about 0.001 mol% or less, or less than, equal to, or greater than about 0.01 mol %,0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45,50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96,97, 98, 99, 99.9, 99.99, or about 99.999 wt % or more of the stabilizerpolymer. The repeating group that is a substituted ethylene can have thestructure:

The variables R², R³, and R⁴ can be independently selected from thegroup consisting of —H, and substituted or unsubstituted(C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups independentlyselected from the group consisting of —O—, —S—, substituted orunsubstituted —NH—, —(CH₂—CH₂—O)_(n1)—, and —(CH₂—CH₂—CH₂—O)_(n1)—,wherein n1 is about 1 to about 10,000 (e.g., about 1 to about 1,000,about 1 to about 100, or about 1 to about 10, or about 2, 3, 4, 5, 6, 7,8, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750, 1,000, 2,000,5,000, 7,500, or about 10,000 or more). The variables R², R³, and R⁴ canbe independently unsubstituted (C₁-C₂₀)hydrocarbyl. The variables R²,R³, and R⁴ can be independently (C₁-C₁₀)alkyl. The variables R², R³, andR⁴ can be —H. The variable R⁵ can be independently selected from thegroup consisting of —C(O)OH, a salt thereof, a substituted orunsubstituted (C₁-C₂₀)hydrocarbyl ester thereof; —C(O)NR¹ ₂, wherein ateach occurrence R¹ is independently selected from the group consistingof a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl; and —CN. Thevariable R⁵ can be —C(O)NR¹ ₂, wherein at each occurrence R¹ can beindependently unsubstituted (C₁-C₂₀)hydrocarbyl. The variable R⁵ can be—C(O)NR¹ ₂, wherein at each occurrence R¹ can be (C₁-C₅)alkyl. Thevariable R⁵ can be —C(O)NR¹ ₂, wherein R¹ can be methyl. The repeatinggroup that is a substituted ethylene can have the structure:

The repeating group that includes an anionic group can form any suitableproportion of the stabilizer polymer, such that the activatorcomposition can be used as described herein, such as about 0.001 mol %to about 99.999 mol % of the stabilizer polymer, about 25 mol % to about99.999 mol %, or about 0.001 mol % or less, or less than, equal to, orgreater than about 0.01 mol %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16,18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88,90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt% or more of the stabilizer polymer. The anionic group in the repeatinggroup can be in the form of an acid or a salt thereof. The repeatinggroup that includes an anionic group can have the structure:

The variable A can be selected from the group consisting of —O— and—NR⁹—. The variable A can be —NR⁹—. The variable R⁹ can be selected fromthe group consisting of —H and (C₁-C₁₀)alkyl. The variable A can be—NH—. The variables R⁶, R⁷, R⁸, R⁹ can be independently selected fromthe group consisting of —H, and a substituted or unsubstituted(C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups independentlyselected from the group consisting of —O—, —S—, substituted orunsubstituted —NH—, —(CH₂—CH₂—O)_(n2)—, and —(CH₂—CH₂—CH₂—O)_(n2)—,wherein n2 is about 1 to about 10,000 (e.g., about 1 to about 1,000,about 1 to about 100, or about 1 to about 10, or about 2, 3, 4, 5, 6, 7,8, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750, 1,000, 2,000,5,000, 7,500, or about 10,000 or more). The variables R⁶, R⁷, R⁸ can beindependently selected from the group consisting of —H and unsubstituted(C₁-C₂₀)hydrocarbyl. The variables R⁶, R⁷, R⁸ can be independentlyselected from the group consisting of —H and unsubstituted(C₁-C₁₀)alkyl. The variables R⁶, R⁷, R⁸ can be —H. The variable L¹ isselected from the group consisting of a bond and a substituted orunsubstituted (C₁-C₅₀)hydrocarbylene interrupted by 0, 1, 2, or 3 groupsindependently selected from the group consisting of —O—, —S—,substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n3)—, and—(CH₂—CH₂—CH₂—O)_(n3)—, wherein n3 is about 1 to about 10,000 (e.g.,about 1 to about 1,000, about 1 to about 100, or about 1 to about 10, orabout 2, 3, 4, 5, 6, 7, 8, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250,500, 750, 1,000, 2,000, 5,000, 7,500, or about 10,000 or more). Thevariable L¹ can be a (C₁-C₂₀)hydrocarbylene that is unsubstituted orsubstituted with a (C₁-C₁₀)alkyl and otherwise unsubstituted. Thevariable L¹ can be a (C₁-C₂₀)alkylene that is unsubstituted orsubstituted with a (C₁-C₅)alkyl and otherwise unsubstituted. Thevariable L¹ can be a (C₁-C₁₀)alkylene that is unsubstituted orsubstituted with a methyl and otherwise unsubstituted. The variable L¹can be a 2-methyl substituted prop-1,2-ylene. The variable L¹ can havethe structure:

The variable AG can be the anionic group. The variable AG can be—S(O)(O)—OH or a salt thereof. The repeating group that includes ananionic group can have the structure:

The —S(O)(O)OH can be in the form of an acid or a salt thereof.

In various embodiments, the stabilizer polymer can include repeatinggroups having the structure:

At each occurrence, the repeating units can independently occur in thedirection shown or in the opposite direction. The repeating units canhave a block or random copolymer arrangement. The variables R², R³, andR⁴ can be independently selected from the group consisting of —H, andsubstituted or unsubstituted (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2,or 3 groups independently selected from the group consisting of —O—,—S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n1)—, and—(CH₂—CH₂—CH₂—O)_(n1)—, wherein n1 is about 1 to about 10,000. Thevariable R⁵ can be independently selected from the group consisting of—C(O)OH, a salt thereof, a substituted or unsubstituted(C₁-C₂₀)hydrocarbyl ester thereof; —C(O)NR¹ ₂, wherein at eachoccurrence R¹ is independently selected from the group consisting of asubstituted or unsubstituted (C₁-C₂₀)hydrocarbyl; and —CN. The variableA can be selected from the group consisting of —O— and —NR⁹—. Thevariables R⁶, R⁷, R⁸, R⁹ can be independently selected from the groupconsisting of —H, and a substituted or unsubstituted (C₁-C₅₀)hydrocarbylinterrupted by 0, 1, 2, or 3 groups independently selected from thegroup consisting of —O—, —S—, substituted or unsubstituted —NH—,—(CH₂—CH₂—O)_(n2)—, and —(CH₂—CH₂—CH₂—O)_(n2)—, wherein n2 is about 1 toabout 10,000. The variable L¹ can be selected from the group consistingof a bond and a substituted or unsubstituted (C₁-C₅₀)hydrocarbyleneinterrupted by 0, 1, 2, or 3 groups independently selected from thegroup consisting of —O—, —S—, substituted or unsubstituted —NH—,—(CH₂—CH₂—O)_(n3)—, and —(CH₂—CH₂—CH₂—O)_(n3)—, wherein n3 is about 1 toabout 10,000. The variable AG can be the anionic group. Repeating groupA can be about 0.001 mol % to about 99.999 mol % of the stabilizerpolymer. Repeating group B can be about 0.001 mol % to about 99.999 mol% of the stabilizer polymer. In various embodiments, repeating groups Aand B together form about 100 mol % of the stabilizer polymer.

In various embodiments, the stabilizer polymer can include repeatinggroups having the structure:

The —S(O)(O)OH group can be in the form of an acid or a salt thereof.Repeating group A can be about 0.001 mol % to about 99.999 mol % of thestabilizer polymer. Repeating group B can be about 0.001 mol % to about99.999 mol % of the stabilizer polymer.

In various embodiments, the stabilizer polymer can further include arepeating unit formed from a vinyl-substituted nitrogen-containing(C₁-C₂₀)heterocycle. The repeating unit formed from a vinyl-substitutednitrogen-containing (C₁-C₂₀)heterocycle can be about 0.001 mol % toabout 99.999 mol % of the stabilizer polymer, about 5 mol % to about 50mol %, or about 0.001 mol % or less, or less than, equal to, or greaterthan about 0.01 mol %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20,25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91,92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt % ormore of the stabilizer polymer. The vinyl group of the vinyl-substitutednitrogen-containing (C₁-C₂₀)heterocycle can be substituted on a nitrogenatom of the nitrogen-containing (C₁-C₂₀)heterocycle. Thevinyl-substituted nitrogen-containing (C₁-C₂₀)heterocycle can beN-vinylpyrrolidone.

The stabilizer polymer can further include an acrylic acid repeatingunit (e.g., a repeating unit that can be formed from polymerized acrylicacid, or formed from a polymerized material that is subsequentlyhydrolyzed to acrylic acid such as an acrylic acid ester or acrylamide).The acrylic acid repeating unit can be about 0.001 mol % to about 99.999mol % of the stabilizer polymer, about 0.001 mol % to about 5 mol %, orabout 0.001 mol % or less, or less than, equal to, or greater than about0.01 mol %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30,35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93,94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt % or more of thestabilizer polymer.

In some embodiments, the repeating group that is a substituted ethyleneis an acrylamide repeating unit, wherein the repeating group thatincludes an anionic group is a 2-acrylamido-2-methylpropane sulfonicacid or salt thereof repeating unit, wherein the stabilizer polymerfurther includes an acrylic acid repeating unit and a N-vinylpyrrolidonerepeating unit. In some embodiments, the acrylamide repeating unit, theAMPS repeating unit, the acrylic acid repeating unit, and theN-vinylpyrrolidone repeating unit can form about 100 mol % of thestabilizer polymer.

In some embodiments, the stabilizer polymer further includes anacrylonitrile repeating unit. The acrylonitrile repeating unit can beabout 0.001 mol % to about 99.999 mol % of the stabilizer polymer, 0.001mol % to about 10 mol %, or about 0.001 mol % or less, or less than,equal to, or greater than about 0.01 mol %, 0.1, 1, 2, 3, 4, 5, 6, 8,10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, orabout 99.999 wt % or more of the stabilizer polymer.

In some embodiments, the repeating group that is a substituted ethyleneis an acrylamide repeating unit, wherein the repeating group thatincludes an anionic group is a 2-acrylamido-2-methylpropane sulfonicacid repeating unit or salt thereof, and the stabilizer polymer furtherincludes an acrylonitrile repeating group. In some embodiments, theacrylamide repeating unit, the AMPS repeating unit, and theacrylonitrile repeating unit, can form about 100 mol % of the stabilizerpolymer.

Other Components.

The cement activator composition, the cement composition, or a mixtureincluding one or both of the same, can include any suitable additionalcomponent in any suitable proportion, such that the cement activatorcomposition or the mixture of cement activator composition and cementcomposition can be used as described herein. Any component listed inthis section can be present or not present in the cement activatorcomposition, the cement composition, or a mixture including one or bothof the same.

In some embodiments, the cement activator composition, the cementcomposition, or a mixture including one or both of the same, includesone or more viscosifiers. The viscosifier can be any suitableviscosifier. The viscosifier can affect the viscosity of the cementactivator composition, the cement composition, or a mixture includingone or both of the same, at any suitable time and location. In someembodiments, the viscosifier provides an increased viscosity at leastone of: before injection into the subterranean formation; at the time ofinjection into the subterranean formation; during travel through atubular disposed in a borehole; once the cement activator composition,the cement composition, or a mixture including one or both of the same,reaches a particular subterranean location; or some period of time afterthe composition or mixture reaches a particular subterranean location.In some embodiments, the viscosifier can be about 0.000,1 wt % to about10 wt % of the cement activator composition, the cement composition, ora mixture including one or both of the same, about 0.004 wt % to about0.01 wt %, or about 0.000,1 wt % or less, 0.000,5 wt %, 0.001, 0.005,0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 wt % ormore.

The viscosifier can include at least one of a substituted orunsubstituted polysaccharide, and a substituted or unsubstitutedpolyalkene (e.g., a polyethylene, wherein the ethylene unit issubstituted or unsubstituted, derived from the corresponding substitutedor unsubstituted ethene), wherein the polysaccharide or polyalkene iscrosslinked or uncrosslinked. The viscosifier can include a polymerincluding at least one repeating unit derived from a monomer selectedfrom the group consisting of ethylene glycol, acrylamide, vinyl acetate,2-acrylamidomethylpropane sulfonic acid or its salts,trimethylammoniumethyl acrylate halide, and trimethylammoniumethylmethacrylate halide. The viscosifier can include a crosslinked gel or acrosslinkable gel. The viscosifier can include at least one of a linearpolysaccharide, and a poly((C₂-C₁₀)alkene), wherein the (C₂-C₁₀)alkeneis substituted or unsubstituted. The viscosifier can include at leastone of poly(acrylic acid) or (C₁-C₅)alkyl esters thereof,poly(methacrylic acid) or (C₁-C₅)alkyl esters thereof, poly(vinylacetate), poly(vinyl alcohol), poly(ethylene glycol), poly(vinylpyrrolidone), polyacrylamide, poly (hydroxyethyl methacrylate),alginate, chitosan, curdlan, dextran, derivatized dextran, emulsan, agalactoglucopolysaccharide, gellan, glucuronan, N-acetyl-glucosamine,N-acetyl-heparosan, hyaluronic acid, kefiran, lentinan, levan, mauran,pullulan, scleroglucan, schizophyllan, stewartan, succinoglycan,xanthan, diutan, welan, starch, derivatized starch, tamarind,tragacanth, guar gum, derivatized guar gum (e.g., hydroxypropyl guar,carboxy methyl guar, or carboxymethyl hydroxypropyl guar), gum ghatti,gum arabic, locust bean gum, karaya gum, cellulose, and derivatizedcellulose (e.g., carboxymethyl cellulose, hydroxyethyl cellulose,carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose, or methylhydroxy ethyl cellulose).

In some embodiments, the viscosifier can include at least one of apoly(vinyl alcohol) homopolymer, poly(vinyl alcohol) copolymer, acrosslinked poly(vinyl alcohol) homopolymer, and a crosslinkedpoly(vinyl alcohol) copolymer. The viscosifier can include a poly(vinylalcohol) copolymer or a crosslinked poly(vinyl alcohol) copolymerincluding at least one of a graft, linear, branched, block, and randomcopolymer of vinyl alcohol and at least one of a substituted orunsubstituted (C₂-C₅₀)hydrocarbyl having at least one aliphaticunsaturated C—C bond therein, and a substituted or unsubstituted(C₂-C₅₀)alkene. The viscosifier can include a poly(vinyl alcohol)copolymer or a crosslinked poly(vinyl alcohol) copolymer including atleast one of a graft, linear, branched, block, and random copolymer ofvinyl alcohol and at least one of vinyl phosphonic acid, vinylidenediphosphonic acid, substituted or unsubstituted2-acrylamido-2-methylpropanesulfonic acid, a substituted orunsubstituted (C₁-C₂₀)alkenoic acid, propenoic acid, butenoic acid,pentenoic acid, hexenoic acid, octenoic acid, nonenoic acid, decenoicacid, acrylic acid, methacrylic acid, hydroxypropyl acrylic acid,acrylamide, fumaric acid, methacrylic acid, hydroxypropyl acrylic acid,vinyl phosphonic acid, vinylidene diphosphonic acid, itaconic acid,crotonic acid, mesoconic acid, citraconic acid, styrene sulfonic acid,allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, and asubstituted or unsubstituted (C₁-C₂₀)alkyl ester thereof. Theviscosifier can include a poly(vinyl alcohol) copolymer or a crosslinkedpoly(vinyl alcohol) copolymer including at least one of a graft, linear,branched, block, and random copolymer of vinyl alcohol and at least oneof vinyl acetate, vinyl propanoate, vinyl butanoate, vinyl pentanoate,vinyl hexanoate, vinyl 2-methyl butanoate, vinyl 3-ethylpentanoate, andvinyl 3-ethylhexanoate, maleic anhydride, a substituted or unsubstituted(C₁-C₂₀)alkenoic substituted or unsubstituted (C₁-C₂₀)alkanoicanhydride, a substituted or unsubstituted (C₁-C₂₀)alkenoic substitutedor unsubstituted (C₁-C₂₀)alkenoic anhydride, propenoic acid anhydride,butenoic acid anhydride, pentenoic acid anhydride, hexenoic acidanhydride, octenoic acid anhydride, nonenoic acid anhydride, decenoicacid anhydride, acrylic acid anhydride, fumaric acid anhydride,methacrylic acid anhydride, hydroxypropyl acrylic acid anhydride, vinylphosphonic acid anhydride, vinylidene diphosphonic acid anhydride,itaconic acid anhydride, crotonic acid anhydride, mesoconic acidanhydride, citraconic acid anhydride, styrene sulfonic acid anhydride,allyl sulfonic acid anhydride, methallyl sulfonic acid anhydride, vinylsulfonic acid anhydride, and an N—(C₁-C₁₀)alkenyl nitrogen-containingsubstituted or unsubstituted (C₁-C₁₀)heterocycle. The viscosifier caninclude a poly(vinyl alcohol) copolymer or a crosslinked poly(vinylalcohol) copolymer including at least one of a graft, linear, branched,block, and random copolymer that includes apoly(vinylalcohol/acrylamide) copolymer, apoly(vinylalcohol/2-acrylamido-2-methylpropanesulfonic acid) copolymer,a poly (acrylamide/2-acrylamido-2-methylpropanesulfonic acid) copolymer,or a poly(vinylalcohol/N-vinylpyrrolidone) copolymer. The viscosifiercan include a crosslinked poly(vinyl alcohol) homopolymer or copolymerincluding a crosslinker including at least one of chromium, aluminum,antimony, zirconium, titanium, calcium, boron, iron, silicon, copper,zinc, magnesium, and an ion thereof. The viscosifier can include acrosslinked poly(vinyl alcohol) homopolymer or copolymer including acrosslinker including at least one of an aldehyde, an aldehyde-formingcompound, a carboxylic acid or an ester thereof, a sulfonic acid or anester thereof, a phosphonic acid or an ester thereof, an acid anhydride,and an epihalohydrin.

In various embodiments, the cement activator composition, the cementcomposition, or a mixture including one or both of the same, can includeone or more crosslinkers. The crosslinker can be any suitablecrosslinker. In some examples, the crosslinker can be incorporated in acrosslinked viscosifier, and in other examples, the crosslinker cancrosslink a crosslinkable material (e.g., downhole). The crosslinker caninclude at least one of chromium, aluminum, antimony, zirconium,titanium, calcium, boron, iron, silicon, copper, zinc, magnesium, and anion thereof. The crosslinker can include at least one of boric acid,borax, a borate, a (C₁-C₃₀)hydrocarbylboronic acid, a(C₁-C₃₀)hydrocarbyl ester of a (C₁-C₃₀)hydrocarbylboronic acid, a(C₁-C₃₀)hydrocarbylboronic acid-modified polyacrylamide, ferricchloride, disodium octaborate tetrahydrate, sodium metaborate, sodiumdiborate, sodium tetraborate, disodium tetraborate, a pentaborate,ulexite, colemanite, magnesium oxide, zirconium lactate, zirconiumtriethanol amine, zirconium lactate triethanolamine, zirconiumcarbonate, zirconium acetylacetonate, zirconium malate, zirconiumcitrate, zirconium diisopropylamine lactate, zirconium glycolate,zirconium triethanol amine glycolate, zirconium lactate glycolate,titanium lactate, titanium malate, titanium citrate, titanium ammoniumlactate, titanium triethanolamine, titanium acetylacetonate, aluminumlactate, and aluminum citrate. In some embodiments, the crosslinker canbe a (C₁-C₂₀)alkylenebiacrylamide (e.g., methylenebisacrylamide), apoly((C₁-C₂₀)alkenyl)-substituted mono- or poly-(C₁-C₂₀)alkyl ether(e.g., pentaerythritol allyl ether), and a poly(C₂-C₂₀)alkenylbenzene(e.g., divinylbenzene). In some embodiments, the crosslinker can be atleast one of alkyl diacrylate, ethylene glycol diacrylate, ethyleneglycol dimethacrylate, polyethylene glycol diacrylate, polyethyleneglycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylatedbisphenol A dimethacrylate, ethoxylated trimethylol propane triacrylate,ethoxylated trimethylol propane trimethacrylate, ethoxylated glyceryltriacrylate, ethoxylated glyceryl trimethacrylate, ethoxylatedpentaerythritol tetraacrylate, ethoxylated pentaerythritoltetramethacrylate, ethoxylated dipentaerythritol hexaacrylate,polyglyceryl monoethylene oxide polyacrylate, polyglyceryl polyethyleneglycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritolhexamethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, pentaerythritol triacrylate, pentaerythritoltrimethacrylate, trimethylol propane triacrylate, trimethylol propanetrimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanedioldimethacrylate. The crosslinker can be about 0.000,01 wt % to about 5 wt% of the cement activator composition, the cement composition, or amixture including one or both of the same, about 0.001 wt % to about0.01 wt %, or about 0.000,01 wt % or less, or about 0.000,05 wt %,0.000,1, 0.000,5, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, orabout 5 wt % or more.

The cement activator composition, the cement composition, or a mixtureincluding one or both of the same, can include any suitable fluid. Forexample, the fluid can be at least one of crude oil, dipropylene glycolmethyl ether, dipropylene glycol dimethyl ether, dipropylene glycolmethyl ether, dipropylene glycol dimethyl ether, dimethyl formamide,diethylene glycol methyl ether, ethylene glycol butyl ether, diethyleneglycol butyl ether, butylglycidyl ether, propylene carbonate,D-limonene, a C₂-C₄₀ fatty acid C₁-C₁₀ alkyl ester (e.g., a fatty acidmethyl ester), tetrahydrofurfuryl methacrylate, tetrahydrofurfurylacrylate, 2-butoxy ethanol, butyl acetate, butyl lactate, furfurylacetate, dimethyl sulfoxide, dimethyl formamide, a petroleumdistillation product of fraction (e.g., diesel, kerosene, napthas, andthe like) mineral oil, a hydrocarbon oil, a hydrocarbon including anaromatic carbon-carbon bond (e.g., benzene, toluene), a hydrocarbonincluding an alpha olefin, xylenes, an ionic liquid, methyl ethylketone, an ester of oxalic, maleic or succinic acid, methanol, ethanol,propanol (iso- or normal-), butyl alcohol (iso-, tert-, or normal-), analiphatic hydrocarbon (e.g., cyclohexanone, hexane), water, brine,produced water, flowback water, brackish water, and sea water. The fluidcan form about 0.001 wt % to about 99.999 wt % of the cement activatorcomposition, the cement composition, or a mixture including one or bothof the same, or about 0.001 wt % or less, 0.01 wt %, 0.1, 1, 2, 3, 4, 5,6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85,90, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt % or more.

The cement activator composition, the cement composition, or a mixtureincluding one or both of the same can include any suitable downholefluid. The cement activator composition can be combined with anysuitable downhole fluid before, during, or after the placement of thecomposition in the subterranean formation or the contacting of thecomposition and the subterranean material. In some examples, the cementactivator composition is combined with a downhole fluid above thesurface, and then the combined composition is placed in a subterraneanformation or contacted with a subterranean material. In another example,the cement activator composition is injected into a subterraneanformation to combine with a downhole fluid, and the combined compositionis contacted with a subterranean material or is considered to be placedin the subterranean formation. The placement of the cement activatorcomposition in the subterranean formation can include contacting thesubterranean material and the mixture including the cement activatorcomposition. Any suitable weight percent of the cement activatorcomposition, the cement composition, or a mixture including one or bothof the same, that is placed in the subterranean formation or contactedwith the subterranean material, can be the downhole fluid, such as about0.001 wt % to about 99.999 wt %, about 0.01 wt % to about 99.99 wt %,about 0.1 wt % to about 99.9 wt %, about 20 wt % to about 90 wt %, orabout 0.001 wt % or less, or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 10,15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98,99, 99.9, 99.99 wt %, or about 99.999 wt % or more of the cementactivator composition, the cement composition, or a mixture includingone or both of the same.

In some embodiments, the cement activator composition, the cementcomposition, or a mixture including one or both of the same, can includeany suitable amount of any suitable material used in a downhole fluid.For example, the cement activator composition, the cement composition,or a mixture including one or both of the same, can include a cement setactivator, such as: a zeolite; an amine such as triethanolamine ordiethanolamine; a silicate such as sodium silicate; zinc formate;calcium acetate; a Group IA or IIA hydroxide such as sodium hydroxide,magnesium hydroxide, or calcium hydroxide; a monovalent salt such assodium chloride; a divalent salt such as calcium chloride; nanosilica(e.g., silica having a particle size of less than or equal to about 100nanometers); a polyphosphate; and combinations thereof). The cementactivator composition, the cement composition, or a mixture includingone or both of the same can include calcium chloride, triethanolamine,sodium silicate, zinc formate, calcium acetate, sodium hydroxide, water,saline, aqueous base, acid, oil, organic solvent, synthetic fluid oilphase, aqueous solution, alcohol or polyol, cellulose, starch,alkalinity control agents, acidity control agents, density controlagents, density modifiers, emulsifiers, dispersants, polymericstabilizers, polyacrylamide, a polymer or combination of polymers,antioxidants, heat stabilizers, foam control agents, solvents, diluents,plasticizer, filler or inorganic particle, pigment, dye, precipitatingagent, oil-wetting agents, set retarding additives, surfactants, gases,weight reducing additives, heavy-weight additives, lost circulationmaterials, filtration control additives, salts (e.g., any suitable salt,such as potassium salts such as potassium chloride, potassium bromide,potassium formate; calcium salts such as calcium chloride, calciumbromide, calcium formate; cesium salts such as cesium chloride, cesiumbromide, cesium formate, or a combination thereof), fibers, thixotropicadditives, breakers, crosslinkers, rheology modifiers, curingaccelerators, curing retarders, pH modifiers, chelating agents, scaleinhibitors, enzymes, resins, water control materials, oxidizers,markers, Portland cement, pozzolana cement, gypsum cement, high aluminacontent cement, slag cement, silica cement, fly ash, metakaolin, shale,zeolite, a crystalline silica compound, amorphous silica, hydratableclays, microspheres, lime, or a combination thereof. Any suitableproportion of the cement activator composition, the cement composition,or a mixture including one or both of the same, can include any optionalcomponent listed in this paragraph, such as about 0.001 wt % to about99.999 wt %, about 0.01 wt % to about 99.99 wt %, about 0.1 wt % toabout 99.9 wt %, about 20 to about 90 wt %, or about 0.001 wt % or less,or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70,80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99 wt %, orabout 99.999 wt % or more of the cement activator composition, thecement composition, or a mixture including one or both of the same.

System or Apparatus.

In various embodiments, the present invention provides a system. Thesystem can be any suitable system that can use or that can be generatedby use of an embodiment of the composition described herein in asubterranean formation, or that can perform or be generated byperformance of a method for using the composition described herein. Thesystem can include a cement activator composition, such as anyembodiment of the cement activator composition described herein. Thesystem can also include a subterranean formation including the cementactivator composition therein. In some embodiments, the cement activatorcomposition in the system can also include a downhole fluid, or thesystem can include a mixture of the cement activator composition anddownhole fluid. In some embodiments, the system can include a tubular,and a pump configured to pump the composition into the subterraneanformation through the tubular. In various embodiments, the systemincludes a mixture that includes the cement activator composition and acement composition.

Various embodiments provide systems and apparatus configured fordelivering the composition described herein to a subterranean locationand for using the composition therein, such as for a cementingoperation. In various embodiments, the system or apparatus can include apump fluidly coupled to a tubular (e.g., any suitable type of oilfieldpipe, such as pipeline, drill pipe, production tubing, and the like),with the tubular including the cement activator composition or a mixtureincluding the same described herein.

The pump can be a high pressure pump in some embodiments. As usedherein, the term “high pressure pump” will refer to a pump that iscapable of delivering a fluid to a subterranean formation (e.g.,downhole) at a pressure of about 1000 psi or greater. In someembodiments, the high pressure pump can be capable of fluidly conveyingparticulate matter into the subterranean formation. Suitable highpressure pumps will be known to one having ordinary skill in the art andcan include floating piston pumps and positive displacement pumps.

In other embodiments, the pump can be a low pressure pump. As usedherein, the term “low pressure pump” will refer to a pump that operatesat a pressure of about 1000 psi or less. In some embodiments, a lowpressure pump can be fluidly coupled to a high pressure pump that isfluidly coupled to the tubular. That is, in such embodiments, the lowpressure pump can be configured to convey the cement activatorcomposition to the high pressure pump. In such embodiments, the lowpressure pump can “step up” the pressure of the cement activatorcomposition before it reaches the high pressure pump.

In some embodiments, the systems or apparatuses described herein canfurther include a mixing tank that is upstream of the pump and in whichthe cement activator composition is formulated or mixed with othermaterials (e.g., with a cement composition or with other additives). Invarious embodiments, the pump (e.g., a low pressure pump, a highpressure pump, or a combination thereof) can convey the cement activatorcomposition or a mixture including the same from the mixing tank orother source of the cement activator composition to the tubular. Inother embodiments, however, the cement activator composition can beformulated offsite and transported to a worksite, in which case thecement activator composition or mixture including the same can beintroduced to the tubular via the pump directly from its shippingcontainer (e.g., a truck, a railcar, a barge, or the like) or from atransport pipeline. In either case, the cement activator composition ormixture including the same can be drawn into the pump, elevated to anappropriate pressure, and then introduced into the tubular for deliveryto the subterranean formation.

FIG. 1 shows an illustrative schematic of systems and apparatuses thatcan deliver embodiments of the cement activator composition or mixtureincluding the same to a subterranean location, according to one or moreembodiments. It should be noted that while FIG. 1 generally depicts aland-based system or apparatus, it is to be recognized that like systemsand apparatuses can be operated in subsea locations as well. Embodimentsof the present invention can have a different scale than that depictedin FIG. 1. As depicted in FIG. 1, system or apparatus 1 can includemixing tank 10, in which an embodiment of the cement activatorcomposition or mixture including the same can be formulated. The cementactivator composition or mixture including the same can be conveyed vialine 12 to wellhead 14, where the composition or mixture including thesame enters tubular 16, with tubular 16 extending from wellhead 14 intosubterranean formation 18. Upon being ejected from tubular 16, thecomposition or mixture including the same can subsequently penetrateinto subterranean formation 18. Pump 20 can be configured to raise thepressure of the composition or mixture including the same to a desireddegree before its introduction into tubular 16. It is to be recognizedthat system or apparatus 1 is merely exemplary in nature and variousadditional components can be present that have not necessarily beendepicted in FIG. 1 in the interest of clarity. In some examples,additional components that can be present include supply hoppers,valves, condensers, adapters, joints, gauges, sensors, compressors,pressure controllers, pressure sensors, flow rate controllers, flow ratesensors, temperature sensors, and the like. Although not depicted inFIG. 1, at least part of the composition can, in some embodiments, flowback to wellhead 14.

It is also to be recognized that the disclosed cement activatorcomposition or mixture including the same can also directly orindirectly affect the various downhole or subterranean equipment andtools that can come into contact with the composition or mixtureincluding the same during operation. Such equipment and tools caninclude wellbore casing, wellbore liner, completion string, insertstrings, drill string, coiled tubing, slickline, wireline, drill pipe,drill collars, mud motors, downhole motors and/or pumps, surface-mountedmotors and/or pumps, centralizers, turbolizers, scratchers, floats(e.g., shoes, collars, valves, and the like), logging tools and relatedtelemetry equipment, actuators (e.g., electromechanical devices,hydromechanical devices, and the like), sliding sleeves, productionsleeves, plugs, screens, filters, flow control devices (e.g., inflowcontrol devices, autonomous inflow control devices, outflow controldevices, and the like), couplings (e.g., electro-hydraulic wet connect,dry connect, inductive coupler, and the like), control lines (e.g.,electrical, fiber optic, hydraulic, and the like), surveillance lines,drill bits and reamers, sensors or distributed sensors, downhole heatexchangers, valves and corresponding actuation devices, tool seals,packers, cement plugs, bridge plugs, and other wellbore isolationdevices or components, and the like. Any of these components can beincluded in the systems and apparatuses generally described above anddepicted in FIG. 1.

Composition for Treatment of a Subterranean Formation.

Various embodiments provide a liquid cement activator composition fortreatment of a subterranean formation. The cement activator compositioncan be any suitable composition that can be used to perform anembodiment of the method for treatment of a subterranean formationdescribed herein.

For example, the liquid cement activator composition can include water,an alkali sulfate salt, a polyphosphate salt, and a stabilizer polymer.The stabilizer polymer can include a repeating group that is an ethylenesubstituted with a group selected from the group consisting of —C(O)OH,a salt thereof, a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl esterthereof; —C(O)NR¹ ₂, wherein at each occurrence R¹ is independentlyselected from the group consisting of a substituted or unsubstituted(C₁-C₂₀)hydrocarbyl; and —CN. At each occurrence the ethylene isindependently further substituted or unsubstituted. The stabilizerpolymer can also include a repeating group that includes an anionicgroup.

In various embodiments, the liquid cement activator composition includeswater, an alkali sulfate salt, a polyphosphate salt, and a stabilizerpolymer. The water can be about 30 wt % to about 95 wt % of the liquidcement activator composition. The alkali sulfate salt can be about 0.001wt % to about 40 wt % of the liquid cement activator composition. Thepolyphosphate salt can be about 0.001 wt % to about 30 wt % of theliquid cement activator composition. The stabilizer polymer can be about0.001 wt % to about 30 wt % of the liquid cement activator composition.The stabilizer polymer can include repeating groups having thestructure:

At each occurrence, the repeating units independently occur in thedirection shown or in the opposite direction. The repeating units canhave a block or random copolymer arrangement. The variables R², R³, andR⁴ can be independently selected from the group consisting of —H, andsubstituted or unsubstituted (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2,or 3 groups independently selected from the group consisting of —O—,—S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n1)—, and—(CH₂—CH₂—CH₂—O)_(n1)—, wherein n1 is about 1 to about 10,000. Thevariable R⁵ can be independently selected from the group consisting of—C(O)OH, a salt thereof, a substituted or unsubstituted(C₁-C₂₀)hydrocarbyl ester thereof; —C(O)NR¹ ₂, wherein at eachoccurrence R¹ is independently selected from the group consisting of asubstituted or unsubstituted (C₁-C₂₀)hydrocarbyl; and —CN. The variableA can be selected from the group consisting of —O— and —NR⁹—. Thevariables R⁶, R⁷, R⁸, R⁹ can be independently selected from the groupconsisting of —H, and a substituted or unsubstituted (C₁-C₅₀)hydrocarbylinterrupted by 0, 1, 2, or 3 groups independently selected from thegroup consisting of —O—, —S—, substituted or unsubstituted —NH—,—(CH₂—CH₂—O)_(n2)—, and —(CH₂—CH₂—CH₂—O)_(n2)—, wherein n2 is about 1 toabout 10,000. The variable L¹ can be selected from the group consistingof a bond and a substituted or unsubstituted (C₁-C₅₀)hydrocarbyleneinterrupted by 0, 1, 2, or 3 groups independently selected from thegroup consisting of —O—, —S—, substituted or unsubstituted —NH—,—(CH₂—CH₂—O)_(n3)—, and —(CH₂—CH₂—CH₂—O)_(n3)—, wherein n3 is about 1 toabout 10,000. The variable AG can be the anionic group. Repeating groupA can be about 0.001 mol % to about 99.999 mol % of the stabilizerpolymer. Repeating group B can be about 0.001 mol % to about 99.999 mol% of the stabilizer polymer.

In some embodiments, the present invention provides a mixture thatincludes an embodiment of the cement activator composition and anembodiment of the cement composition described herein, such as apumice-containing cement composition (e.g., a pozzolanacement-containing cement composition). In various embodiments, thepresent invention provides a cured produce of the mixture including thecement activator composition and the cement composition.

Method for Preparing a Composition for Treatment of a SubterraneanFormation.

In various embodiments, the present invention provides a method forpreparing a composition for treatment of a subterranean formation. Themethod can be any suitable method that produces a composition describedherein. For example, the method can include forming a liquid cementactivator composition for treatment of a subterranean formation, such asany embodiment of a cement activator composition described herein. Theliquid cement activator composition can include water, an alkali sulfatesalt, a polyphosphate salt, and a stabilizer polymer. The stabilizerpolymer can be any embodiment of a stabilizer polymer described herein.The stabilizer polymer can include a repeating group that is an ethylenesubstituted with a group selected from the group consisting of —C(O)OH,a salt thereof, a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl esterthereof; —C(O)NR¹ ₂, wherein at each occurrence R¹ is independentlyselected from the group consisting of a substituted or unsubstituted(C₁-C₂₀)hydrocarbyl; and —CN. At each occurrence the ethylene isindependently further substituted or unsubstituted. The stabilizerpolymer can also include a repeating group that includes an anionicgroup.

EXAMPLES

Various embodiments of the present invention can be better understood byreference to the following Examples which are offered by way ofillustration. The present invention is not limited to the Examples givenherein.

General. Liquiment® 5581F is a polycarboxylated ether dispersant,available from BASF Corporation. SA-1015™ suspending agent is anadditive available from Halliburton Corporation. Halad®-344 is acopolymer derived from acrylamido-methyl-propane sulfonate (AMPS) anddimethylacrylamide (DMA), available from Halliburton Corporation.Halad®-200 is a copolymer derived from acrylamido-methyl-propanesulfonate (AMPS), dimethylacrylamide (DMA), N-vinyl pyrrolidone, andacrylic acid, available from Halliburton Corporation. Halad®-413 is acopolymer derived from acrylamide, acrylonitrile, and2-acrylamido-2-methylpropane sulfonic acid (AMPS), with the AMPS groupsgrafted on lignite, available from Halliburton Corporation. LAP-1 ispoly(vinyl alcohol), available from Halliburton Corporation. HZ30™ ispolyacrylamide that may partially hydrolyze upon storage or upon contactwith aqueous media, available from Halliburton Corporation. Thedesignation of wt % bwP refers to the percent by weight of pozzolan inan 800 g liquid slurry sample of a pumice cement (434.82 g, 54.35 wt %).The pozzolan was the only pumice present in the liquid slurry sample ofthe pumice cement.

Example 1 Sample A. Activating System without an AMPS/DMA Copolymer(Comparative)

The activator system was mixed in the order and concentrations shown inTable 1. Activator was mixed in an American Petroleum Institute (API)blender in approximately 240 g of H₂O, at approximately 1300-1500 rpm.

TABLE 1 Order of addition Material Mass Wt % bwP 1 sodium 18 g 0.9%hexametaphosphate (SHMP) 2 Na₂SO₄ 27 g 1.35% 3 Liquiment ® 5581F 42 g2.1%

Immediate separation after mixing occurred. The top layer appeared afterthe solution was allowed to sit for approximately 24 hrs. Appearance ofthe cloudy, yellow top layer seemed to be dependent upon the amount oftime that the solution was allowed to sit undisturbed. The second layerof the solution was very difficult to re-homogenize when agitated. FIG.2 illustrates a photograph of the activator system after 7 days

Example 2 Sample B. Activating System with an AMPS/DMA Copolymer

The activator system was mixed in the order and concentrations shown inTable 2. The activator was mixed in an API blender in approximately 240g of H₂O, at approximately 1300-1500 rpm.

TABLE 2 Order of addition Material Mass Wt % bwP 1 SHMP 18 g 0.9% 2Na₂SO₄ 27 g 1.35% 3 Liquiment ® 5581F 42 g 2.1% 4 Halad ®-344 10 g 0.5%

The sample remained homogenous from time mixing stopped to the 7-daymark at which this picture was taken. Brookfield viscosity measurementsindicated a stable slurry at around 400 cP. FIG. 3 illustrates aphotograph of the activating system after 7 days.

Example 3 Sample C. Activating System with AMPS/Acrylamide/AcrylonitrileCopolymer and a Viscosifier

The activator system was mixed in the order and concentrations shown inTable 3. The activator was mixed an in API blender in approximately 240g of H₂O, at approximately 1300-1500 rpm.

TABLE 3 Order of addition Material Mass Wt % bwP 1 SHMP 18 g 0.9% 2Na₂SO₄ 27 g 1.35% 3 Liquiment ® 5581F 42 g 2.1% 4 Halad ®-413 10 g 0.5%

The sample showed signs of separation 15-20 mins after mixing asindicated by the darker layer in the bottom of the picture. Clearseparation between top and bottom layers was visible after 3 days. FIG.4 illustrates a photograph of the activating system after 3 days. Thedark bottom-most layer indicates the beginning of a darker layer formingfrom the much larger, brighter top layer.

Example 4 Sample D. Activating System with an AMPS/DMA Copolymer and aViscosifier

The activator system was mixed in the order and concentrations shown inTable 4. The activator was mixed in an API blender in approximately 240g of H₂O, at approximately 1300-1500 rpm.

TABLE 4 Order of addition Material Mass Wt % bwP 1 SA-1015 ™ 2 g 0.1%suspending agent 2 SHMP 18 g 0.9% 3 Na₂SO₄ 27 g 1.35% 4 Liquiment ®5581F 42 g 2.1%

SA1015™ suspending agent was added initially and mixed for 2-3 minutesuntil yielding completely and producing a thick gel. Addition ofLiquiment® 5581F significantly thickened the solution during mixing.Additional shear (2000 rpm) was used to reintroduce a vortex duringmixing. The mixture begin to slowly separate after mixing. After 3 days,the top cloudy layer appeared, and the middle layer was becomingdistinct from the clear bottom layer. The second layer of the solutionwas very difficult to re-homogenize when agitated. FIG. 5 illustrates aphotograph of the activating system after 3 days.

Example 5 Sample E. Activating System with an AMPS/DMA Copolymer and aViscosifier

The activator system was mixed in the order and concentrations shown inTable 5. The activator was mixed in an API blender in approximately 240g of H₂O, at approximately 1300-1500 rpm.

TABLE 5 Order of addition Material Mass Wt % bwP 1 SHMP 18 g 0.9% 2Na₂SO₄ 27 g 1.35% 3 Liquiment ® 5581F 42 g 2.1% 4 SA-1015 ™ 2 g 0.1%suspending agent

The system begin to slowly separate after mixing. The sample showed athird, top layer at around 24 hours after initial mixing. When comparedto the previous activator (Sample D) of the exact same formulation andorder of addition, much more distinct separation is visible that iscreated as a result of time. The second layer of the solution was verydifficult to re-homogenize when agitated. FIG. 6 illustrates aphotograph of the activating system after 4 days.

Example 6 Sample F. Activating System with an AMPS/DMA Copolymer and aViscosifier

The activator system was mixed in the order and concentrations shown inTable 6. The activator was mixed an in API blender in approximately 240g of H₂O, at approximately 1300-1500 rpm.

TABLE 6 Order of addition Material Mass Wt % 1 SA-1015 ™ 0.24 g 0.1% byweight of suspending agent water (BWOW) 2 SHMP 18 g 0.9% bwP 3 Na₂SO₄ 27g 1.35% bwP 4 Liquiment ® 5581F 42 g 2.1% bwP

The sample separated immediately after mixing. Sample was showing toplayer of foam 1-3 hours after mixing. Less SA1015™ suspending agentseems to expedite the separation process, as well as create anotherlayer on the top of the solution. The second layer of the solution wasvery difficult to re-homogenize when agitated. FIG. 7 illustrates aphotograph of the activating system after 3 days. The fourth layer atthe top of the solution was not present in other samples.

Example 7 Sample G. Activating System without an AMPS/DMA Copolymer(Comparative)

The activator system was mixed in the order and concentrations shown inTable 7. The activator was mixed an in API blender in approximately 240g of H₂O, at approximately 1300-1500 rpm.

TABLE 7 Order of addition Material Mass Wt % bwP 1 Liquiment ® 5581F 42g 2.1% 2 SHMP 18 g 0.9% 3 Na₂SO₄ 27 g 1.35%

The sample separated immediately upon completion of mixing. A smallthird layer of foam appeared at the top of the solution. The secondlayer of the solution was very difficult to re-homogenize when agitated.FIG. 8 illustrates a photograph of the activating system after 3 days.

Example 8 Sample H. Activating System without an AMPS/DMA Copolymer(Comparative)

The activator system was mixed in the order and concentrations shown inTable 8. The activator was mixed an in API blender in approximately 240g of H₂O, at approximately 1300-1500 rpm.

TABLE 8 Order of addition Material Mass Wt % bwP 1 Liquiment ® 5581F 42g 2.1% 2 Na₂SO₄ 27 g 1.35% 3 SHMP 18 g 0.9%

The sample was extremely thick upon completion of mixing. The sampleseparated slowly, with a large portion of the solution occupied byLiquiment® 5581F. Small amounts of Liquiment® 5581F remained in thebottom layer. This was not seen in any of the previous samples. Thesecond layer of the solution was very difficult to re-homogenize whenagitated. FIG. 9 illustrates a photograph of the activating system after3 days. Small amounts of Liquiment® 5581F were visible in the bottomlayer.

Example 9 Sample I. Activating System with anAMPS/Acrylamide/N-Vinylpyrrolidone/Acrylic Acid Copolymer

The activator system was mixed in the order and concentrations shown inTable 9. The activator was mixed an in API blender in approximately 240g of H₂O, at approximately 1300-1500 rpm.

TABLE 9 Order of addition Material Mass Wt % bwP 1 SHMP 18 g 0.9% 2Na₂SO₄ 27 g 1.35% 3 Liquiment ® 5581F 42 g 2.1% 4 Halad ®-200 10 g 0.5%

The sample remained homogenous from the time mixing stopped to at leastthe 48 hour mark. FIG. 10 illustrates a photograph of the activatingsystem after 24 hours.

Example 10 Sample J. Activating System with a Poly(Vinyl Alcohol)Polymer (Comparative)

The activator system was mixed in the order and concentrations shown inTable 10. The activator was mixed an in API blender in approximately 240g of H₂O, at approximately 1300-1500 rpm.

TABLE 10 Order of addition Material Mass Wt % bwP 1 SHMP 18 g 0.9% 2Na₂SO₄ 27 g 1.35%  3 Liquiment ® 5581F 42 g 2.1% 4 LAP-1 10 g 0.5%

The sample separated immediately. The sample separated into 4 distinctlayers by the 24 hour mark. FIG. 11 illustrates a photograph of theactivating system after 24 hours.

Example 11 Sample K. Activating System with an Acrylamide-Acrylic AcidCopolymer (Comparative)

The activator system was mixed according to standard procedure, in theorder and concentrations shown in Table 11. The activator was mixed anin API blender with 200 g of water to account for the 40 g of waterpresent in the HZ-30 solution (activity of HZ-30 was 20%; therefore, 50g of HZ-30 solution was needed to place 10 g of HZ-30 polymer in theactivator). HZ-30 solution was added to the water before mixing began.Blender speed was approximately 1300-1500 rpm.

TABLE 11 Order of addition Material Mass Wt % bwP 1 HZ-30 + H₂O 10 gHZ-30 + 40 g 0.5% H₂O 2 SHMP 18 g 0.9% 3 Na₂SO₄ 27 g 1.35% 4 Liquiment ®5581F 42 g 2.1%

The sample separated immediately. The sample separated into 4 distinctlayers by the 24 hour mark. FIG. 12 illustrates a photograph of theactivating system, after 24 hours.

Example 12 Analysis of Examples 1-11

Example A is a conventional sodium sulfate and sodium hexametaphosphateactivating system with polycarboxylate ether dispersant Liquiment® 5581F(BASF). As can be observed from the image in FIG. 2, this systemimmediately separates into distinct phases or layers and does not retainhomogeneity. Furthermore, it is difficult to homogenize with agitationafter the separating. To determine whether the order of addition of theingredients influenced the system homogeneity, Examples G and H wereprepared. Even though Examples G and H were prepared by adding theingredients in different sequences, separation was still observed.Separation in Example H was slower, but still within 1-2 hours frompreparation.

Example B is the same formula of sodium sulfate, sodiumhexametaphosphate, and Liquiment® 5581F as described for Example A, buthas 0.5% by weight of pumice (bwP) Halad®-344 (copolymer of AMPS anddimethyl acrylamide) added to it. As shown in FIG. 3, the resultingsuspension remained homogenous without exhibiting phase separation for 7days. Both Examples A and B were prepared in the same manner. Rheologymeasurements were performed on Examples A and B with a LV SeriesBrookfield Viscometer using a #2 spindle at 60 rpms. The averageviscosity of several runs for each was 114 cP for Example A and 399 cPfor Example B. This result prompted the consideration that a viscosityincrease, provided by the addition of co-polymer, may be responsible forimproving the suspension, homogeneity, and overall stability of theactivator system.

To investigate the influence of viscosity on the activator systemstability, Examples D, E, and F were prepared. These examples containedof SA1015™ suspending agent as a viscosifier. If the stabilizing effectwas derived from an increase in system viscosity that enabled greateruniformity and homogeneity, addition of the suspension aid should alsoprovide stabilization. It was found that regardless of (1) theconcentration of suspension aid or (2) the sequence of addition of thesuspension aid separation could not be suppressed. The rate ofseparation for each example ranged from days (3 days, D) to hours(within 24 hours, E) to minutes (immediate separation, F). None of theExamples D, E, or F remained homogenous with addition of suspension aid.FIGS. 5, 6, and 7 provide images of the separated activator systems forExamples D, E, and F, respectively.

The focus of the investigation then shifted to the interaction of theactivator system with the polymeric fluid loss additive. Examples C, I,J, and K were prepared and mixed in the same proportions as was ExampleB. Example C contained Halad®-413 (Acrylonitrile, acrylamide, AMPSgrafted on lignite), Example I contained Halad®-200 (heteropolymer ofAMPS, acrylamide, N-vinylpyrrolidone, and acrylic acid), Example Jcontained LAP-1 (polyvinyl alcohol), and Example K contained HZ™-30(polyacrylamide). Example C showed signs of separation immediately afterpreparation with a small bottom layer becoming visible. After 3 days,separation of two distinct layers was clearly visible. Example I behavedidentically to Example B, remaining stable after preparation and atleast 2 days. Examples J and K separated immediately after preparationinto distinct layers. Through these observations, it was evident thataddition of Halad®-200, which, in comparison to the other polymerstested in this series, is most like Halad®-344 in chemical composition,stabilizes the activator system to enable long shelf life.

Although not definitive at present, the experiments suggest that anacrylic copolymer with charged functionality, when added to the sodiumsulfate and sodium hexametaphosphate activator system, creates the moststable combination. Halad®-413, which contains AMPS, separated the leastin comparison to the rest of the polymer additives tested; however, thelignite component may very well prevent the desired level of stability.

Addition of a copolymeric additive like Halad®-344 also provided thebenefit of imparting fluid loss control to the activated cement slurrywithout the disadvantages of premixing fluid loss additive with the drycement mix. The following data shown in Tables 12 and 13 provides acomparison of an Example A activator system with the more stable ExampleB activator system.

TABLE 12 Example A vs. Example B. Activator Pump Time Fluid Loss 24-hrCrush Type (hr:mins) (cc) (psi) Example A 6:10 82 689 Example B 6:28 80658

TABLE 13 Examples A and B. 6D and 3D refer to the rheometric decayvalues at 3 and 6 rpm, respectively. The designations “up” and “down”refer to whether the measurement was taken as RPM was increasing (“up”)or decreasing (“down”). The data given in the Table shows viscometerdial readings from a Fann 35 viscometer with a Fann Yield Stress Adapterand a no. 1 spring. RPM 300 200 100 60 30 6 6D 3 3D Example A  80° F. Up48 32 17 11 6 2.5 1 Down 48 31 16 9.5 5 2 0.5 1 0.5 130° F. Up 27 18 9 64 1.5 1 Down 27 16 8.5 5.5 4 1 0.5 1 0.5 180° F. Up 21 13 7 5 3 1.5 1Down 21 13 6 4.5 3 1.5 0.5 1 5.5 Example B  80° F. Up 47 32 17 11 6 3 1Down 47 30 15 9.5 5 2 0.5 1 0.5 130° F. Up 27 17 9 6 4 2 1 Down 27 168.5 6 4 1.5 0.5 1 0.5 180° F. Up 21 13 7 5 3 1.5 1 Down 21 12 6 4 3 10.5 1 0.5

The data indicates that the activator system of the invention (ExampleB) gives as good or better results in pump time, fluid loss, and 24-hcompressive strength measurements when compared to the conventionalactivator system (Example A). FANN® yield stress adapter (FYSA) rheologymeasurements taken on activated cement slurries at temperatures of 80°F., 130° F., and 180° F. were comparable for both Example A and Bactivator systems. Thus, incorporation of the polymeric additive to theactivator system lends desirable properties to the cement slurry and setcement matrix, and also causes no detriment to the activated slurryrheology. This is on top of the stabilizing benefit the polymer provideswhich enables longer shelf life and improved handling. Data collectionwas performed according to API 10B-2/ISO 10426-2 Recommended Practicefor Testing Well Cements.

The terms and expressions that have been employed are used as terms ofdescription and not of limitation, and there is no intention in the useof such terms and expressions of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of theembodiments of the present invention. Thus, it should be understood thatalthough the present invention has been specifically disclosed byspecific embodiments and optional features, modification and variationof the concepts herein disclosed may be resorted to by those of ordinaryskill in the art, and that such modifications and variations areconsidered to be within the scope of embodiments of the presentinvention.

Additional Embodiments

The following exemplary embodiments are provided, the numbering of whichis not to be construed as designating levels of importance:

Embodiment 1 provides a method of treating a subterranean formation, themethod comprising:

placing in the subterranean formation a liquid cement activatorcomposition comprising

-   -   water;    -   an alkali sulfate salt;    -   a polyphosphate salt; and    -   a stabilizer polymer comprising        -   a repeating group that is an ethylene substituted with a            group selected from the group consisting of            -   —C(O)OH, a salt thereof, a substituted or unsubstituted                (C₁-C₂₀)hydrocarbyl ester thereof,            -   —C(O)NR¹ ₂, wherein at each occurrence R¹ is                independently selected from the group consisting of a                substituted or unsubstituted (C₁-C₂₀)hydrocarbyl,            -   —CN, and            -   combinations thereof;            -   wherein at each occurrence the ethylene is independently                further substituted or unsubstituted, and        -   a repeating group that comprises an anionic group.

Embodiment 2 provides the method of Embodiment 1, wherein the methodfurther comprises obtaining or providing the composition, wherein theobtaining or providing of the composition occurs above-surface.

Embodiment 3 provides the method of any one of Embodiments 1-2, whereinthe method further comprises obtaining or providing the composition,wherein the obtaining or providing of the composition occurs in thesubterranean formation.

Embodiment 4 provides the method of any one of Embodiments 1-3, furthercomprising combining the cement activator composition with a cementcomposition.

Embodiment 5 provides the method of Embodiment 4, wherein the combiningof the cement activator composition and the cement composition occursabove-surface, wherein placing the liquid cement activator compositionin the subterranean formation comprises placing a mixture of the liquidcement activator composition and the cement composition in thesubterranean formation.

Embodiment 6 provides the method of any one of Embodiments 4-5, whereinthe combining of the cement activator composition and the cementcomposition occurs in the subterranean formation.

Embodiment 7 provides the method of any one of Embodiments 4-6, whereinabout 0.001 wt % to about 99.999 wt % of the combination of the cementactivator composition and the cement composition is the cement activatorcomposition.

Embodiment 8 provides the method of any one of Embodiments 4-7, whereinabout 10 wt % to about 50 wt % of the combination of the cementactivator composition and the cement composition is the cement activatorcomposition.

Embodiment 9 provides the method of any one of Embodiments 4-8, whereinthe cement composition comprises Portland cement, pozzolana cement,gypsum cement, high alumina content cement, slag cement, silica cement,or a combination thereof.

Embodiment 10 provides the method of any one of Embodiments 4-9, whereinthe cement composition comprises pozzolana cement, wherein the activatorcomposition is about 60% to about 95% of the weight of pozzolana in thecement composition.

Embodiment 11 provides the method of any one of Embodiments 4-10,wherein the cement composition comprises pozzolana-lime cement.

Embodiment 12 provides the method of any one of Embodiments 4-11,wherein the cement composition is a delayed-set cement composition.

Embodiment 13 provides the method of any one of Embodiments 4-12,further comprising curing the combination of the cement activatorcomposition and the cement composition.

Embodiment 14 provides the method of any one of Embodiments 1-13,wherein the water is about 30 wt % to about 95 wt % of the cementactivator composition.

Embodiment 15 provides the method of any one of Embodiments 1-14,wherein the water is about 60 wt % to about 80 wt % of the cementactivator composition.

Embodiment 16 provides the method of any one of Embodiments 1-15,wherein the alkali sulfate salt is about 0.001 wt % to about 40 wt % ofthe cement activator composition.

Embodiment 17 provides the method of any one of Embodiments 1-16,wherein the alkali sulfate salt is about 1 wt % to about 15 wt % of thecement activator composition.

Embodiment 18 provides the method of any one of Embodiments 1-17,wherein the alkali sulfate salt comprises potassium sulfate, calciumsulfate, lithium sulfate, sodium sulfate, or a combination thereof.

Embodiment 19 provides the method of any one of Embodiments 1-18,wherein the alkali sulfate salt is sodium sulfate.

Embodiment 20 provides the method of any one of Embodiments 1-19,wherein the polyphosphate salt is about 0.001 wt % to about 30 wt % ofthe cement activator composition.

Embodiment 21 provides the method of any one of Embodiments 1-20,wherein the polyphosphate salt is about 1 wt % to about 15 wt % of thecement activator composition.

Embodiment 22 provides the method of any one of Embodiments 1-21,wherein the polyphosphate salt comprises a polymeric metaphosphate salt,a phosphate salt, or a combination thereof.

Embodiment 23 provides the method of any one of Embodiments 1-22,wherein the polyphosphate salt comprises sodium hexametaphosphate,sodium trimetaphosphate, sodium tetrametaphosphate, sodiumpentametaphosphate, sodium heptametaphosphate, sodium octametaphosphate,and combinations thereof.

Embodiment 24 provides the method of any one of Embodiments 1-23,wherein the polyphosphate salt is sodium hexametaphosphate.

Embodiment 25 provides the method of any one of Embodiments 1-24,wherein the cement activator composition further comprises a dispersant.

Embodiment 26 provides the method of Embodiment 25, wherein thedispersant is about 0.001 wt % to about 40 wt % of the cement activatorcomposition.

Embodiment 27 provides the method of any one of Embodiments 25-26,wherein the dispersant is about 1 wt % to about 25 wt % of the cementactivator composition.

Embodiment 28 provides the method of any one of Embodiments 25-27,wherein the dispersant comprises a superplasticizing dispersant, asulfonated-formaldehyde-based dispersant, a polycarboxylated etherdispersant, or a combination thereof.

Embodiment 29 provides the method of any one of Embodiments 25-28,wherein the dispersant is a polycarboxylated ether.

Embodiment 30 provides the method of any one of Embodiments 1-29,wherein the stabilizer polymer is about 0.001 wt % to about 30 wt % ofthe cement activator composition.

Embodiment 31 provides the method of any one of Embodiments 1-30,wherein the stabilizer polymer is about 0.1 wt % to about 10 wt % of thecement activator composition.

Embodiment 32 provides the method of any one of Embodiments 1-31,wherein the repeating group that is a substituted ethylene is about0.001 mol % to about 99.999 mol % of the stabilizer polymer.

Embodiment 33 provides the method of any one of Embodiments 1-32,wherein the repeating group that is a substituted ethylene is about0.001 mol % to about 25 mol % of the stabilizer polymer.

Embodiment 34 provides the method of any one of Embodiments 1-33,wherein the repeating group that is a substituted ethylene has thestructure:

wherein

-   -   R², R³, and R⁴ are independently selected from the group        consisting of —H, and substituted or unsubstituted        (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups        independently selected from the group consisting of —O—, —S—,        substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n1)—, and        —(CH₂—CH₂—CH₂—O)_(n1)—, wherein n1 is about 1 to about 10,000;    -   R⁵ is independently selected from the group consisting of        -   C(O)OH, a salt thereof, a substituted or unsubstituted            (C₁-C₂₀)hydrocarbyl ester thereof,        -   —C(O)NR¹ ₂, wherein at each occurrence R¹ is independently            selected from the group consisting of a substituted or            unsubstituted (C₁-C₂₀)hydrocarbyl, and        -   —CN.

Embodiment 35 provides the method of Embodiment 34, wherein R², R³, andR⁴ are independently unsubstituted (C₁-C₂₀)hydrocarbyl.

Embodiment 36 provides the method of any one of Embodiments 34-35,wherein R², R³, and R⁴ are independently (C₁-C₁₀)alkyl.

Embodiment 37 provides the method of any one of Embodiments 34-36,wherein R², R³, and R⁴ are —H.

Embodiment 38 provides the method of any one of Embodiments 34-37,wherein R⁵ is —C(O)NR¹ ₂, wherein at each occurrence R¹ is independentlyunsubstituted (C₁-C₂₀)hydrocarbyl.

Embodiment 39 provides the method of any one of Embodiments 34-38,wherein R⁵ is —C(O)NR¹ ₂, wherein at each occurrence R¹ is (C₁-C₅)alkyl.

Embodiment 40 provides the method of any one of Embodiments 34-39,wherein R⁵ is —C(O)NR¹ ₂, wherein R¹ is methyl.

Embodiment 41 provides the method of any one of Embodiments 34-40,wherein the repeating group that is a substituted ethylene has thestructure:

Embodiment 42 provides the method of any one of Embodiments 1-41,wherein the repeating group that comprises an anionic group is about0.001 mol % to about 99.999 mol % of the stabilizer polymer.

Embodiment 43 provides the method of any one of Embodiments 1-42,wherein the repeating group that comprises an anionic group is about 25mol % to about 99.999 mol % of the stabilizer polymer.

Embodiment 44 provides the method of any one of Embodiments 1-43,wherein the anionic group in the repeating group that comprises theanionic group is in the form of an acid or a salt thereof.

Embodiment 45 provides the method of any one of Embodiments 1-44,wherein the repeating group that comprises an anionic group has thestructure:

wherein

-   -   A is selected from the group consisting of —O— and —NR⁹—,    -   R⁶, R⁷, R⁸, R⁹ are independently selected from the group        consisting of —H, and a substituted or unsubstituted        (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups        independently selected from the group consisting of —O—, —S—,        substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n2)—, and        —(CH₂—CH₂—CH₂—O)_(n2)—, wherein n2 is about 1 to about 10,000,    -   L¹ is selected from the group consisting of a bond and a        substituted or unsubstituted (C₁-C₅₀)hydrocarbylene interrupted        by 0, 1, 2, or 3 groups independently selected from the group        consisting of —O—, —S—, substituted or unsubstituted —NH—,        —(CH₂—CH₂—O)_(n3)—, and —(CH₂—CH₂—CH₂—O)_(n3)—, wherein n3 is        about 1 to about 10,000, and    -   AG is the anionic group.

Embodiment 46 provides the method of Embodiment 45, wherein A is —NR⁹—.

Embodiment 47 provides the method of Embodiment 46, wherein R⁹ isselected from the group consisting of —H and (C₁-C₁₀)alkyl.

Embodiment 48 provides the method of any one of Embodiments 46-47,wherein A is —NH—.

Embodiment 49 provides the method of any one of Embodiments 45-48,wherein R⁶, R⁷, R⁸ are independently selected from the group consistingof —H and unsubstituted (C₁-C₂₀)hydrocarbyl.

Embodiment 50 provides the method of any one of Embodiments 45-49,wherein R⁶, R⁷, R⁸ are independently selected from the group consistingof —H and unsubstituted (C₁-C₁₀)alkyl.

Embodiment 51 provides the method of any one of Embodiments 45-50,wherein R⁶, R⁷, R⁸ are —H.

Embodiment 52 provides the method of any one of Embodiments 45-51,wherein L¹ is (C₁-C₂₀)hydrocarbylene that is unsubstituted orsubstituted with a (C₁-C₁₀)alkyl and otherwise unsubstituted.

Embodiment 53 provides the method of any one of Embodiments 45-52,wherein L¹ is (C₁-C₂₀)alkylene that is unsubstituted or substituted witha (C₁-C₅)alkyl and otherwise unsubstituted.

Embodiment 54 provides the method of any one of Embodiments 45-53,wherein L¹ is (C₁-C₁₀)alkylene that is unsubstituted or substituted witha methyl and otherwise unsubstituted.

Embodiment 55 provides the method of any one of Embodiments 45-54,wherein L¹ is a 2-methyl substituted prop-1,2-ylene.

Embodiment 56 provides the method of any one of Embodiments 45-55,wherein L¹ has the structure:

Embodiment 57 provides the method of any one of Embodiments 45-56,wherein AG is —S(O)(O)—OH or a salt thereof.

Embodiment 58 provides the method of any one of Embodiments 1-57,wherein the repeating group that comprises an anionic group has thestructure:

wherein the —S(O)(O)OH is in the form of an acid or a salt thereof.

Embodiment 59 provides the method of any one of Embodiments 1-58,wherein the stabilizer polymer comprises repeating groups having thestructure:

wherein

-   -   at each occurrence, the repeating units independently occur in        the direction shown or in the opposite direction,    -   the repeating units have a block or random copolymer        arrangement,    -   R², R³, and R⁴ are independently selected from the group        consisting of —H, and substituted or unsubstituted        (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups        independently selected from the group consisting of —O—, —S—,        substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n1)—, and        —(CH₂—CH₂—CH₂—O)_(n1)—, wherein n1 is about 1 to about 10,000,    -   R⁵ is independently selected from the group consisting of        -   —C(O)OH, a salt thereof, a substituted or unsubstituted            (C₁-C₂₀)hydrocarbyl ester thereof,        -   —C(O)NR¹ ₂, wherein at each occurrence R¹ is independently            selected from the group consisting of a substituted or            unsubstituted (C₁-C₂₀)hydrocarbyl, and        -   —CN,    -   A is selected from the group consisting of —O— and —NR⁹—,    -   R⁶, R⁷, R⁸, R⁹ are independently selected from the group        consisting of —H, and a substituted or unsubstituted        (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups        independently selected from the group consisting of —O—, —S—,        substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n2)—, and        —(CH₂—CH₂—CH₂—O)_(n2)—, wherein n2 is about 1 to about 10,000,    -   L¹ is selected from the group consisting of a bond and a        substituted or unsubstituted (C₁-C₅₀)hydrocarbylene interrupted        by 0, 1, 2, or 3 groups independently selected from the group        consisting of —O—, —S—, substituted or unsubstituted —NH—,        —(CH₂—CH₂—O)_(n3)—, and —(CH₂—CH₂—CH₂—O)_(n3)—, wherein n3 is        about 1 to about 10,000,    -   AG is the anionic group,    -   repeating group A is about 0.001 mol % to about 99.999 mol % of        the stabilizer polymer, and    -   repeating group B is about 0.001 mol % to about 99.999 mol % of        the stabilizer polymer.

Embodiment 60 provides the method of any one of Embodiments 1-59,wherein the stabilizer polymer comprises repeating groups having thestructure:

wherein

-   -   the —S(O)(O)OH group is in the form of an acid or a salt        thereof,    -   repeating group A is about 0.001 mol % to about 99.999 mol % of        the stabilizer polymer, and    -   repeating group B is about 0.001 mol % to about 99.999 mol % of        the stabilizer polymer.

Embodiment 61 provides the method of any one of Embodiments 1-60,wherein the stabilizer polymer further comprises a repeating unit formedfrom a vinyl-substituted nitrogen-containing (C₁-C₂₀)heterocycle.

Embodiment 62 provides the method of Embodiment 61, wherein therepeating unit formed from a vinyl-substituted nitrogen-containing(C₁-C₂₀)heterocycle is about 0.001 mol % to about 99.999 mol % of thestabilizer polymer.

Embodiment 63 provides the method of any one of Embodiments 61-62,wherein the repeating unit formed from a vinyl-substitutednitrogen-containing (C₁-C₂₀)heterocycle is about 5 mol % to about 50 mol% of the stabilizer polymer.

Embodiment 64 provides the method of any one of Embodiments 61-63,wherein the vinyl group of the vinyl-substituted nitrogen-containing(C₁-C₂₀)heterocycle is substituted on a nitrogen atom of thenitrogen-containing (C₁-C₂₀)heterocycle.

Embodiment 65 provides the method of any one of Embodiments 61-64,wherein the vinyl-substituted nitrogen-containing (C₁-C₂₀)heterocycle isN-vinylpyrrolidone.

Embodiment 66 provides the method of any one of Embodiments 1-65,wherein the stabilizer polymer further comprises an acrylic acidrepeating unit.

Embodiment 67 provides the method of Embodiment 66, wherein the acrylicacid repeating unit is about 0.001 mol % to about 55 mol % of thestabilizer polymer.

Embodiment 68 provides the method of any one of Embodiments 1-67,wherein the repeating group that is a substituted ethylene is anacrylamide repeating unit, wherein the repeating group that comprises ananionic group is a 2-acrylamido-2-methylpropane sulfonic acid or saltthereof repeating unit, wherein the stabilizer polymer further comprisesan acrylic acid repeating unit and a N-vinylpyrrolidone repeating unit.

Embodiment 69 provides the method of any one of Embodiments 1-68,wherein the stabilizer polymer further comprises an acrylonitrilerepeating unit.

Embodiment 70 provides the method of Embodiment 69, wherein theacrylonitrile repeating unit is about 0.001 mol % to about 10 mol % ofthe stabilizer polymer.

Embodiment 71 provides the method of any one of Embodiments 69-70,wherein the repeating group that is a substituted ethylene is anacrylamide repeating unit, wherein the repeating group that comprises ananionic group is a 2-acrylamido-2-methylpropane sulfonic acid repeatingunit or salt thereof.

Embodiment 72 provides the method of any one of Embodiments 1-71,wherein the cement activator composition further comprises calciumchloride, triethanolamine, sodium silicate, zinc formate, calciumacetate, sodium hydroxide, water, saline, aqueous base, oil, organicsolvent, synthetic fluid oil phase, aqueous solution, alcohol or polyol,cellulose, starch, alkalinity control agent, acidity control agent,density control agent, density modifier, emulsifier, dispersant,polymeric stabilizer, polyacrylamide, polymer or combination ofpolymers, antioxidant, heat stabilizer, foam control agent, solvent,diluent, plasticizer, filler or inorganic particle, pigment, dye,precipitating agent, oil-wetting agent, set retarding additive,surfactant, corrosion inhibitor, gas, weight reducing additive,heavy-weight additive, lost circulation material, filtration controladditive, salt, fiber, thixotropic additive, breaker, crosslinker, gas,rheology modifier, curing accelerator, curing retarder, pH modifier,chelating agent, scale inhibitor, enzyme, resin, water control material,polymer, oxidizer, a marker, Portland cement, pozzolana cement, gypsumcement, high alumina content cement, slag cement, silica cement, flyash, metakaolin, shale, zeolite, a crystalline silica compound,amorphous silica, fibers, a hydratable clay, microspheres, pozzolanlime, or a combination thereof.

Embodiment 73 provides the method of any one of Embodiments 1-72,wherein the placing of the cement activator composition in thesubterranean formation comprises pumping the cement activatorcomposition through a tubular disposed in a wellbore and into thesubterranean formation.

Embodiment 74 provides a system for performing the method of any one ofEmbodiments 1-73, the system comprising:

a tubular disposed in the subterranean formation; and

a pump configured to pump the cement activator composition in thesubterranean formation through the tubular.

Embodiment 75 provides a method of treating a subterranean formation,the method comprising:

placing in the subterranean formation a liquid cement activatorcomposition comprising

-   -   water that is about 30 wt % to about 95 wt % of the liquid        cement activator composition;    -   an alkali sulfate salt that is about 0.001 wt % to about 40 wt %        of the liquid cement activator composition;    -   a polyphosphate salt that is about 0.001 wt % to about 30 wt %        of the liquid cement activator composition; and    -   a stabilizer polymer that is about 0.001 wt % to about 30 wt %        of the liquid cement activator composition, the stabilizer        polymer comprising repeating groups having the structure:

-   -   wherein        -   at each occurrence, the repeating units independently occur            in the direction shown or in the opposite direction,        -   the repeating units have a block or random copolymer            arrangement,        -   R², R³, and R⁴ are independently selected from the group            consisting of —H, and substituted or unsubstituted            (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups            independently selected from the group consisting of —O—,            —S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n1)—,            and —(CH₂—CH₂—CH₂—O)_(n1)—, wherein n1 is about 1 to about            10,000,        -   R⁵ is independently selected from the group consisting of            -   —C(O)OH, a salt thereof, a substituted or unsubstituted                (C₁-C₂₀)hydrocarbyl ester thereof,            -   —C(O)NR¹ ₂, wherein at each occurrence R¹ is                independently selected from the group consisting of a                substituted or unsubstituted (C₁-C₂₀)hydrocarbyl, and            -   —CN,        -   A is selected from the group consisting of —O— and —NR⁹—,        -   R⁶, R⁷, R⁸, R⁹ are independently selected from the group            consisting of —H, and a substituted or unsubstituted            (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups            independently selected from the group consisting of —O—,            —S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n2)—,            and —(CH₂—CH₂—CH₂—O)_(n2)—, wherein n2 is about 1 to about            10,000,        -   L¹ is selected from the group consisting of a bond and a            substituted or unsubstituted (C₁-C₅₀)hydrocarbylene            interrupted by 0, 1, 2, or 3 groups independently selected            from the group consisting of —O—, —S—, substituted or            unsubstituted —NH—, —(CH₂—CH₂—O)_(n3)—, and            —(CH₂—CH₂—CH₂—O)_(n3)—, wherein n3 is about 1 to about            10,000,        -   AG is the anionic group,        -   repeating group A is about 0.001 mol % to about 25 mol % of            the stabilizer polymer, and        -   repeating group B is about 25 mol % to about 99.999 mol % of            the stabilizer polymer.

Embodiment 76 provides a method of treating a subterranean formation,the method comprising:

placing in the subterranean formation a liquid cement activatorcomposition comprising

-   -   water that is about 30 wt % to about 95 wt % of the liquid        cement activator composition;    -   an alkali sulfate salt that is about 0.001 wt % to about 40 wt %        of the liquid cement activator composition;    -   a polyphosphate salt that is about 0.001 wt % to about 30 wt %        of the liquid cement activator composition; and    -   a stabilizer polymer that is about 0.001 wt % to about 30 wt %        of the liquid cement activator composition, the stabilizer        polymer comprising repeating groups having the structure:

-   -   wherein        -   at each occurrence, the repeating units independently occur            in the direction shown or in the opposite direction,        -   the repeating units have a block or random copolymer            arrangement,        -   the —S(O)(O)OH group is in the form of an acid or a salt            thereof,        -   repeating group A is about 0.001 mol % to about 25 mol % of            the stabilizer polymer, and        -   repeating group B is about 25 mol % to about 99.999 mol % of            the stabilizer polymer.

Embodiment 77 provides a system comprising:

a tubular disposed in a subterranean formation; and

a pump configured to pump a liquid cement activator composition in thesubterranean formation through the tubular, wherein the cement activatorcomposition comprises

-   -   water;    -   an alkali sulfate salt;    -   a polyphosphate salt; and    -   a stabilizer polymer comprising        -   a repeating group that is an ethylene substituted with a            group selected from the group consisting of            -   —C(O)OH, a salt thereof, a substituted or unsubstituted                (C₁-C₂₀)hydrocarbyl ester thereof,            -   —C(O)NR¹ ₂, wherein at each occurrence R¹ is                independently selected from the group consisting of a                substituted or unsubstituted (C₁-C₂₀)hydrocarbyl,            -   —CN, and            -   combinations thereof,        -   wherein at each occurrence the ethylene is independently            further substituted or unsubstituted, and        -   a repeating group that comprises an anionic group.

Embodiment 78 provides a liquid cement activator composition fortreatment of a subterranean formation, the cement activator compositioncomprising:

water;

an alkali sulfate salt;

a polyphosphate salt; and

a stabilizer polymer comprising

-   -   a repeating group that is an ethylene substituted with a group        selected from the group consisting of        -   —C(O)OH, a salt thereof, a substituted or unsubstituted            (C₁-C₂₀)hydrocarbyl ester thereof,        -   —C(O)NR¹ ₂, wherein at each occurrence R¹ is independently            selected from the group consisting of a substituted or            unsubstituted (C₁-C₂₀)hydrocarbyl,        -   —CN, and        -   combinations thereof,        -   wherein at each occurrence the ethylene is independently            further substituted or unsubstituted, and        -   a repeating group that comprises an anionic group.

Embodiment 79 provides a liquid cement activator composition fortreatment of a subterranean formation, the cement activator compositioncomprising:

water that is about 30 wt % to about 95 wt % of the liquid cementactivator composition;

an alkali sulfate salt that is about 0.001 wt % to about 40 wt % of theliquid cement activator composition;

a polyphosphate salt that is about 0.001 wt % to about 30 wt % of theliquid cement activator composition; and

a stabilizer polymer that is about 0.001 wt % to about 30 wt % of theliquid cement activator composition, the stabilizer polymer comprisingrepeating groups having the structure:

wherein

-   -   at each occurrence, the repeating units independently occur in        the direction shown or in the opposite direction,    -   the repeating units have a block or random copolymer        arrangement,    -   R², R³, and R⁴ are independently selected from the group        consisting of —H, and substituted or unsubstituted        (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups        independently selected from the group consisting of —O—, —S—,        substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n1)—, and        —(CH₂—CH₂—CH₂—O)_(n1)—, wherein n1 is about 1 to about 10,000,    -   R⁵ is independently selected from the group consisting of        -   —C(O)OH, a salt thereof, a substituted or unsubstituted            (C₁-C₂₀)hydrocarbyl ester thereof,        -   —C(O)NR¹ ₂, wherein at each occurrence R¹ is independently            selected from the group consisting of a substituted or            unsubstituted (C₁-C₂₀)hydrocarbyl, and        -   —CN,    -   A is selected from the group consisting of —O— and —NR⁹—,    -   R⁶, R⁷, R⁸, R⁹ are independently selected from the group        consisting of —H, and a substituted or unsubstituted        (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups        independently selected from the group consisting of —O—, —S—,        substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n2)—, and        —(CH₂—CH₂—CH₂—O)_(n2)—, wherein n2 is about 1 to about 10,000,    -   L¹ is selected from the group consisting of a bond and a        substituted or unsubstituted (C₁-C₅₀)hydrocarbylene interrupted        by 0, 1, 2, or 3 groups independently selected from the group        consisting of —O—, —S—, substituted or unsubstituted —NH—,        —(CH₂—CH₂—O)_(n3)—, and —(CH₂—CH₂—CH₂—O)_(n3)—, wherein n3 is        about 1 to about 10,000,    -   AG is the anionic group,    -   repeating group A is about 0.001 mol % to about 25 mol % of the        stabilizer polymer, and    -   repeating group B is about 25 mol % to about 99.999 mol % of the        stabilizer polymer.

Embodiment 80 provides a method of preparing a composition for treatmentof a subterranean formation, the method comprising:

forming a liquid cement activator composition for treatment of asubterranean formation, the cement activator composition comprising:

-   -   water;    -   an alkali sulfate salt;    -   a polyphosphate salt; and    -   a stabilizer polymer comprising        -   a repeating group that is an ethylene substituted with a            group selected from the group consisting of            -   —C(O)OH, a salt thereof, a substituted or unsubstituted                (C₁-C₂₀)hydrocarbyl ester thereof,            -   —C(O)NR¹ ₂, wherein at each occurrence R¹ is                independently selected from the group consisting of a                substituted or unsubstituted (C₁-C₂₀)hydrocarbyl,            -   CN, and            -   combinations thereof,    -   wherein at each occurrence the ethylene is independently further        substituted or unsubstituted, and        -   a repeating group that comprises an anionic group.

Embodiment 81 provides the method, system, or composition of any one orany combination of Embodiments 1-80 optionally configured such that allelements or options recited are available to use or select from.

What is claimed is:
 1. A method of treating a subterranean formation, comprising: placing a pre-formulated liquid cement activator composition in the subterranean formation, the pre-formulated liquid cement activator composition having fluid loss control properties in addition to liquid cement activation properties and comprising: water; about 1 wt % to about 15 wt % of an alkali sulfate salt comprising potassium sulfate, lithium sulfate, sodium sulfate, or any combination thereof; a polyphosphate salt; and a stabilizer polymer comprising: a repeating group that is an ethylene substituted with a group selected from the group consisting of: —C(O)OH, a salt thereof, a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl ester thereof, —C(O)NR^(l) ₂, wherein at each occurrence R¹ is independently selected from the group consisting of a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl, —CN, and any combination thereof; wherein at each occurrence the ethylene is independently further substituted or unsubstituted, and a repeating group that comprises an anionic group; stabilizing the homogeneity of the alkali sulfate salt and the polyphosphate salt in the pre-formulated liquid cement activator composition with the stabilizer polymer; and combining the pre-formulated liquid cement activator composition with a set-delayed cement composition comprising pozzolana-lime cement and excluding fluid loss control agents; and activating the set-delayed cement composition with the alkali sulfate salt and the polyphosphate salt in the pre-formulated liquid cement activator composition, whereby the set-delayed cement composition cures.
 2. The method of claim 1, wherein the combining of the pre-formulated liquid cement activator composition and the set-delayed cement composition occurs in the subterranean formation, and wherein about 10 wt % to about 50 wt % of the combination of the pre-formulated liquid cement activator composition and the cement composition is the pre-formulated liquid cement activator composition.
 3. The method of claim 1, wherein the set-delayed cement composition further comprises Portland cement, gypsum cement, high alumina content cement, slag cement, silica cement, or any combination thereof.
 4. The method of claim 1, wherein the pre-formulated liquid cement activator is composition about 60% to about 95% of the weight of pozzolana in the set-delayed cement composition.
 5. The method of claim 1, wherein the polyphosphate salt is about 1 wt % to about 15 wt % of the pre-formulated liquid cement activator composition, and wherein the polyphosphate salt comprises sodium hexametaphosphate, sodium trimetaphosphate, sodium tetrametaphosphate, sodium pentametaphosphate, sodium heptametaphosphate, sodium octametaphosphate, or any combination thereof.
 6. The method of claim 1, wherein the pre-formulated liquid cement activator composition further comprises a dispersant, wherein the dispersant is about 1 wt % to about 25 wt % of the liquid cement activator composition, and wherein the dispersant comprises a superplasticizing dispersant, a sulfonated-formaldehyde-based dispersant, a polycarboxylated ether dispersant, or any combination thereof.
 7. The method of claim 1, wherein the repeating group that is a substituted ethylene has the structure:

wherein R², R³, and R⁴ are independently selected from the group consisting of —H, and substituted or unsubstituted (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups independently selected from the group consisting of —O—, —S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n1)—, and —(CH₂—CH₂—CH₂—O)_(n1)—, wherein n1 is 1 to about 10,000; R⁵ is independently selected from the group consisting of: —C(O)OH, a salt thereof, a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl ester thereof, —C(O)NR¹ ₂, wherein at each occurrence R¹ is independently selected from the group consisting of a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl, —CN, and any combination thereof.
 8. The method of claim 7, wherein R², R³, and R⁴ are independently —H or (C₁-C₁₀)alkyl, and wherein R⁵ is —C(O)NR¹ ₂, wherein at each occurrence R¹ is (C₁-C₅)alkyl.
 9. The method of claim 7, wherein the repeating group that is a substituted ethylene has the structure:


10. The method of claim 1, wherein the repeating group that comprises an anionic group has the structure:

wherein: A is selected from the group consisting of —O— and —NR⁹—, R⁶, R⁷, R⁸, R⁹ are independently selected from the group consisting of —H, and a substituted or unsubstituted (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups independently selected from the group consisting of —O—, —S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n2)—, and —(CH₂—CH₂—CH₂—O)_(n2)—, wherein n2 is 1 to about 10,000, L¹ is selected from the group consisting of a bond and a substituted or unsubstituted (C₁-C₅₀)hydrocarbylene interrupted by 0, 1, 2, or 3 groups independently selected from the group consisting of —O—, —S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n3)—, and —(CH₂—CH₂—CH₂—O)_(n3)—, wherein n3 is 1 to about 10,000, and AG is the anionic group.
 11. The method of claim 10, wherein R⁶, R⁷, R⁸ are independently selected from the group consisting of —H and unsubstituted (C₁-C₁₀)alkyl, and wherein A is —NR⁹—, and wherein R⁹ is selected from the group consisting of —H and (C₁-C₁₀)alkyl.
 12. The method of claim 10, wherein L¹ is a 2-methyl substituted prop-1,2-ylene.
 13. The method of claim 1, wherein the repeating group that comprises an anionic group has the structure:

wherein the —S(O)(O)OH is in the form of an acid or a salt thereof.
 14. The method of claim 1, wherein the stabilizer polymer comprises repeating groups having the structure:

wherein: at each occurrence, the repeating units independently occur in the direction shown or in the opposite direction, the repeating units have a block or random copolymer arrangement, R², R³, and R⁴ are independently selected from the group consisting of —H, and substituted or unsubstituted (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups independently selected from the group consisting of —O—, —S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n1)—, and —(CH₂—CH₂—CH₂—O)_(n1)—, wherein n1 is 1 to about 10,000, R⁵ is independently selected from the group consisting of: —C(O)OH, a salt thereof, a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl ester thereof, C(O)NR¹ ₂, wherein at each occurrence R¹ is independently selected from the group consisting of a substituted or unsubstituted (C₁-C₂₀)hydrocarbyl, CN, and any combination thereof, A is selected from the group consisting of —O— and —NR⁹—, R⁶, R⁷, R⁸, R⁹ are independently selected from the group consisting of —H, and a substituted or unsubstituted (C₁-C₅₀)hydrocarbyl interrupted by 0, 1, 2, or 3 groups independently selected from the group consisting of —O—, —S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n2)—, and —(CH₂—CH₂—CH₂—O)_(n2)—, wherein n2 is 1 to about 10,000, L¹ is selected from the group consisting of a bond and a substituted or unsubstituted (C₁-C₅₀)hydrocarbylene interrupted by 0, 1, 2, or 3 groups independently selected from the group consisting of —O—, —S—, substituted or unsubstituted —NH—, —(CH₂—CH₂—O)_(n3)—, and —(CH₂—CH₂—CH₂—O)_(n3)—, wherein n3 is 1 to about 10,000, AG is the anionic group, repeating group A is about 0.001 mol % to about 99.999 mol % of the stabilizer polymer, and repeating group B is about 0.001 mol % to about 99.999 mol % of the stabilizer polymer.
 15. The method of claim 1, wherein the stabilizer polymer comprises repeating groups having the structure:

wherein: the —S(O)(O)OH group is in the form of an acid or a salt thereof, repeating group A is about 0.001 mol % to about 99.999 mol % of the stabilizer polymer, and repeating group B is about 0.001 mol % to about 99.999 mol % of the stabilizer polymer.
 16. The method of claim 1, wherein the stabilizer polymer further comprises a repeating unit formed from a vinyl-substituted nitrogen-containing (C₁-C₂₀)heterocycle is about 5 mol % to about 50 mol % of the stabilizer polymer.
 17. The method of claim 1, wherein the repeating group that is a substituted ethylene is an acrylamide repeating unit, wherein the repeating group that comprises an anionic group is a 2-acrylamido-2-methylpropane sulfonic acid or salt thereof repeating unit, wherein the stabilizer polymer further comprises an acrylic acid repeating unit and a N-vinylpyrrolidone repeating unit. 